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At least 55 records · Page 3

Enhanced photoresponse of conformal TiO{sub 2}/Ag nanorod array-based Schottky photodiodes fabricated via successive glancing angle and atomic layer deposition

In this study, the authors demonstrate a proof of concept nanostructured photodiode fabrication method via successive glancing angle deposition (GLAD) and atomic layer deposition (ALD). The fabricated metal-semiconductor nanorod (NR) arrays offer enhanced photoresponse compared to conventional planar thin-film counterparts. Silver (Ag) metallic NR arrays were deposited on Ag-film/Si templates by utilizing GLAD. Subsequently, titanium dioxide (TiO{sub 2}) was deposited conformally on Ag NRs via ALD. Scanning electron microscopy studies confirmed the successful formation of vertically aligned Ag NRs deposited via GLAD and conformal deposition of TiO{sub 2} on Ag NRs via ALD. Following the growth of TiO{sub 2} on Ag NRs, aluminum metallic top contacts were formed to complete the fabrication of NR-based Schottky photodiodes. Nanostructured devices exhibited a photo response enhancement factor of 1.49 × 10{sup 2} under a reverse bias of 3 V.

36 MATERIALS SCIENCE↗

Electrochemically Grown Ultrathin Platinum Nanosheet Electrodes with Ultralow Loadings for Energy-Saving and Industrial-Level Hydrogen Evolution

Nanostructured catalyst-integrated electrodes with remarkably reduced catalyst loadings, high catalyst utilization and facile fabrication are urgently needed to enable cost-effective, green hydrogen production via proton exchange membrane electrolyzer cells (PEMECs). Herein, benefitting from a thin seeding layer, bottom-up grown ultrathin Pt nanosheets (Pt-NSs) were first deposited on thin Ti substrates for PEMECs via a fast, template- and surfactant-free electrochemical growth process at room temperature, showing highly uniform Pt surface coverage with ultralow loadings and vertically well-aligned nanosheet morphologies. Combined with an anode-only Nafion 117 catalyst-coated membrane (CCM), the Pt-NS electrode with an ultralow loading of 0.015 mg Pt cm -2 demonstrates superior cell performance to the commercial CCM (3.0 mg Pt cm -2 ), achieving 99.5% catalyst savings and more than 237-fold higher catalyst utilization. The remarkable performance with high catalyst utilization is mainly due to the vertically well-aligned ultrathin nanosheets with good surface coverage exposing abundant active sites for the electrochemical reaction. Overall, this study not only paves a new way for optimizing the catalyst uniformity and surface coverage with ultralow loadings but also provides new insights into nanostructured electrode design and facile fabrication for highly efficient and low-cost PEMECs and other energy storage/conversion devices.

42 ENGINEERING↗

Resolving Triblock Terpolymer Morphologies by Vapor-Phase Infiltration

The spontaneous formation of well-organized three-dimensional (3D) nanostructures from self-assembled block copolymers (BCPs) holds promise for nanofabrication and lithography. The addition of a third block to BCPs provides access to a plethora of 3D geometries, but it remains difficult to resolve the geometry of such “three-color” structures when there is low contrast between the polymeric components at length scales of a few nm. Here, we apply vapor-phase infiltration synthesis to a silicon-containing triblock terpolymer, poly(1,1- dimethyl silacyclobutane-b-styrene-b-lactide) (PDMSB-b-PS-b-PLA or DSL) to distinguish the 3D microdomain morphologies of the two organic blocks, PLA and PS. Selective infiltration of ZnO within the PLA microdomains reveals morphologies consisting of three-color lamellae or lamellae combined with vertically aligned core-shell cylinders, depending on the volume fractions of each block. The infiltration produces ZnO nanoparticles throughout the 260 nm thickness of the DSL film, generating 3D nanocomposites containing ZnO and SiO x . These results provide a strategy for synthesizing multicomponent 3D nanostructures as well as visualizing the phase behavior of multi-block copolymers.

36 MATERIALS SCIENCE↗

Impact of surface morphology of Si substrate on performance of Si/ZnO heterojunction devices grown by atomic layer deposition technique

In this paper, the authors have investigated the structural, optical, and electrical characteristics of silicon nanowire (SiNW)/zinc oxide (ZnO) core–shell nanostructure heterojunctions and compared their characteristics with Si/ZnO planar heterojunctions to investigate the effect of surface morphology of Si substrate in the characteristics of Si/ZnO heterojunction devices. In this work, ZnO thin film was conformally deposited on both p-type 〈100〉 planar Si substrate and substrate with vertically aligned SiNW arrays by atomic layer deposition (ALD) method. The x-ray diffraction spectra show that the crystalline structures of Si/ZnO heterojunctions are having (101) preferred orientation, whereas vertically oriented SiNW/ZnO core–shell heterojunctions are having (002)-oriented wurtzite crystalline structures. The photoluminescence (PL) spectra of Si/ZnO heterojunctions show a very sharp single peak at 377 nm, corresponding to the bandgap of ZnO material with no other defect peaks in visible region; hence, these devices can have applications only in UV region. On the other hand, SiNW/ZnO heterojunctions are having band-edge peak at 378 nm along with a broad emission band, spreading almost throughout the entire visible region with a peak around 550 nm. Therefore, ALD-grown SiNW/ZnO heterojunctions can emit green and red light simultaneously. Reflectivity measurement of the heterojunctions further confirms the enhancement of visible region peak in the PL spectra of SiNW/ZnO heterojunctions, as the surface of the SiNW/ZnO heterojunctions exhibits extremely low reflectance (<3%) in the visible wavelength region compared to Si/ZnO heterojunctions (>20%). The current–voltage characteristics of both Si/ZnO and SiNW/ZnO heterojunctions are measured with large area ohmic contacts on top and bottom of the structure to compare the electrical characteristics of the devices. Due to large surface to-volume ratio of SiNW/ZnO core–shell heterojunction devices, the output current rating is about 130 times larger compared to their planar version at 2 V forward bias voltage. This higher output current rating can be exploited for fabricating high-performance nanoelectronic and optoelectronic devices in near future.

42 ENGINEERING↗

Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors

While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS 2 ) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g -1 in an Li-rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg -1 —the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg -1 with stable operation over 10 000 cycles. In conclusion, a flexible solid-state supercapacitor prepared by transferring the TiS 2 –VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min.

36 MATERIALS SCIENCE↗

Ultra-sharp plasmonic resonances from monopole optical nanoantenna phased arrays

Diffractively coupled plasmonic resonances possess both ultra-sharp linewidths and giant electric field enhancement around plasmonic nanostructures. They can be applied to create a new generation of sensors, detectors, and nano-optical devices. However, all current designs require stringent index-matching at the resonance condition that limits their applicability. Here, we propose and demonstrate that it is possible to relieve the index-matching requirement and to induce ultra-sharp plasmon resonances in an ordered vertically aligned optical nano-antenna phased array by transforming a dipole resonance to a monopole resonance with a mirror plane. Due to the mirror image effect, the monopole resonance not only retained the dipole features but also enhanced them. The engineered resonances strongly suppressed the radiative decay channel, resulting in a four-order of magnitude enhancement in local electric field and a Q-factor greater than 200.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au–TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Furthermore, two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

42 ENGINEERING↗

Morphological and spectroscopic studies on the vertically aligned zinc oxide nanorods grown on low and high temperature deposited seed layer

Vertically aligned zinc oxide nanorods were grown on low and high temperature deposited aluminium doped zinc oxide seed layer by hydrothermal method and annealed to improve crystallinity. The morphology of the seed layer and the grown nanorods were studied by field emission scanning electron microscopy characterization technique. The properties of the zinc oxide nanorods were analyzed using laser spectroscopic studies. Resonant Raman spectroscopy reveals the unique increase in the A{sub 1}(LO) mode of vibration with increase in count. The luminescence property of the nanorods was studied with photoluminescence spectrometer. The vertically aligned zinc oxide nanorods show, the very high band edge emission in the ultraviolet region of the electromagnetic spectrum.

36 MATERIALS SCIENCE↗

Electrical properties of Mg doped ZnO nanostructure annealed at different temperature

In this work, ZincOxide (ZnO) nanostructures doped with Mg were successfully grown on the glass substrate. Magnesium (Mg) metal element was added in the ZnO host which acts as a doping agent. Different temperature in range of 250°C to 500°C was used in order to investigate the effect of annealing temperature of ZnO thin films. Field Emission Scanning Electron Microscopy (FESEM) was used to investigate the physical characteristic of ZnO thin films. FESEM results have revealed that ZnO nanorods were grown vertically aligned. The structural properties were determined by using X-Ray Diffraction (XRD) analysis. XRD results showed Mg doped ZnO thin have highest crystalinnity at 500°C annealing temperature. The electrical properties were investigating by using Current-Voltage (I-V) measurement. I-V measurement showed the electrical properties were varied at different annealing temperature. The annealing temperature at 500°C has the highest electrical conductance properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nitride-Oxide-Metal Heterostructure with Self-Assembled Core–Shell Nanopillar Arrays: Effect of Ordering on Magneto-Optical Properties

Magneto-optical (MO) coupling incorporates photon-induced change of magnetic polarization that can be adopted in ultrafast switching, optical isolators, mode convertors, and optical data storage components for advanced optical integrated circuits. However, integrating plasmonic, magnetic, and dielectric properties in one single material system poses challenges since one natural material can hardly possess all these functionalities. Here, co-deposition of a three-phase heterostructure composed of a durable conductive nitride matrix with embedded core–shell vertically aligned nanopillars, is demonstrated. Additionally, the unique coupling between ferromagnetic NiO core and atomically sharp plasmonic Au shell enables strong MO activity out-of-plane at room temperature. Further, a template growth process is applied, which significantly enhances the ordering of the nanopillar array. The ordered nanostructure offers two schemes of spin polarization which result in stronger antisymmetry of Kerr rotation. The presented complex hybrid metamaterial platform with strong magnetic and optical anisotropies is promising for tunable and modulated all-optical-based nanodevices.

36 MATERIALS SCIENCE↗

Salt-Induced Self-Assembly of Bacteria on Nanowire Arrays

Studying bacteria-nanostructure interactions is crucial to gaining controllable interfacing of biotic and abiotic components in advanced biotechnologies. For bioelectrochemical systems, tunable cell-electrode architectures offer a path toward improving performance and discovering emergent properties. As such, Sporomusa ovata cells cultured on vertical silicon nanowire arrays formed filamentous cells and aligned parallel to the nanowires when grown in increasing ionic concentrations. In this work, we propose a model describing the kinetic and the thermodynamic driving forces of bacteria-nanowire interactions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Vertically Aligned Single-Crystalline CoFe 2 O 4 Nanobrush Architectures with High Magnetization and Tailored Magnetic Anisotropy

Micrometer-tall vertically aligned single-crystalline CoFe 2 O 4 nanobrush architectures with extraordinarily large aspect ratio have been achieved by the precise control of a kinetic and thermodynamic non-equilibrium pulsed laser epitaxy process. Direct observations by scanning transmission electron microscopy reveal that the nanobrush crystal is mostly defect-free by nature, and epitaxially connected to the substrate through a continuous 2D interface layer. In contrast, periodic dislocations and lattice defects such as anti-phase boundaries and twin boundaries are frequently observed in the 2D interface layer, suggesting that interface misfit strain relaxation under a non-equilibrium growth condition plays a critical role in the self-assembly of such artificial architectures. Further, magnetic property measurements have found that the nanobrushes exhibit a saturation magnetization value of 6.16 μB/f.u., which is much higher than the bulk value. The discovery not only enables insights into an effective route for fabricating unconventional high-quality nanostructures, but also demonstrates a novel magnetic architecture with potential applications in nanomagnetic devices.

36 MATERIALS SCIENCE↗

Size-controlled synthesis of anatase nanobrush structures with higher crystal density

Highlights: • Application of AAO as template for TiO{sub 2} nanowires synthesis. • Non-hydrolytic sol-gel method as an implementation of TiO{sub 2} into AAO template. • Vertical anchorage of TiO2 nanowires to the polymer support. • Photocatalytic oxidation of methyl orange correlate with geometric surface area of TiO{sub 2}. - Abstract: Titanium dioxide was synthesized in multistep process applying of AAO (Anode Aluminum Oxide) as a template. The TiO{sub 2} nanowires were obtained by deposition of titanium precursors inside the pores of AAO membranes (non-hydrolytic sol-gel technique), calcined at 875 K with subsequent removal of alumina matrix by leaching it with phosphoric acid. During the AAO synthesis, it was proved that the electrical work can serve as the unified factor influencing the amount of formed AAO. The diameters of obtained titania nanowires were consequence of used AAO membranes. The higher density of titania elementary cell was observed for all synthesized nanostructures. It was confirmed by XRD and SAED measurements. The TiO{sub 2} nanowires attached vertically to polymer disc (50 mm diameter) were used in photocatalytic decomposition of methyl orange. All nanomaterials showed ten times higher photocatalytic activity than P-25. High photoactivity of obtained material is related to external area of vertically aligned titania nanowires.

36 MATERIALS SCIENCE↗

Core-shell metallic alloy nanopillars-in-dielectric hybrid metamaterials with magneto-plasmonic coupling

Combining plasmonic and magnetic properties, namely magneto-plasmonic coupling, inspires great research interest and the search for magneto-plasmonic nanostructure becomes considerably critical. In this work, we designed a nanopillar-in-matrix structure with core–shell alloyed nanopillars for both BaTiO 3 (BTO)-Au 0.5 Co 0.5 (AuCo) and BTO-Au 0.25 Cu 0.25 Co 0.25 Ni 0.25 (AuCuCoNi) hybrid systems, i.e., ferromagnetic alloy cores (e.g., Co or CoNi) with plasmonic shells (e.g., Au or Au/Cu). These core–shell alloy nanopillars are uniformly embedded into a dielectric BTO matrix to form a vertically aligned nanocomposite (VAN) structure. Both hybrid systems present excellent epitaxial quality and interesting multi-functionality, e.g., high magnetic anisotropy, magneto-optical coupling response, tailorable plasmonic resonance wavelength, tunable hyperbolic properties and strong optical anisotropy. These alloyed nanopillars-in-matrix designs provide enormous potential for complex hybrid material designs with multi-functionality and demonstrate strong interface enabled magneto-plasmonic coupling along with plasmonic and magnetic performance.

36 MATERIALS SCIENCE↗

Reducing leakage current and enhancing polarization in multiferroic 3D super-nanocomposites by microstructure engineering

Abstract Multiferroic materials have generated great interest due to their potential as functional device materials. Nanocomposites have been increasingly used to design and generate new functionalities by pairing dissimilar ferroic materials, though the combination often introduces new complexity and challenges unforeseeable in single-phase counterparts. The recently developed approaches to fabricate 3D super-nanocomposites (3D‐sNC) open new avenues to control and enhance functional properties. In this work, we develop a new 3D‐sNC with CoFe 2 O 4 (CFO) short nanopillar arrays embedded in BaTiO 3 (BTO) film matrix via microstructure engineering by alternatively depositing BTO:CFO vertically-aligned nanocomposite layers and single-phase BTO layers. This microstructure engineering method allows encapsulating the relative conducting CFO phase by the insulating BTO phase, which suppress the leakage current and enhance the polarization. Our results demonstrate that microstructure engineering in 3D‐sNC offers a new bottom–up method of fabricating advanced nanostructures with a wide range of possible configurations for applications where the functional properties need to be systematically modified.

36 MATERIALS SCIENCE↗

Exploring the Spatial Control of Topotactic Phase Transitions Using Vertically Oriented Epitaxial Interfaces

Engineering oxygen vacancy formation and distribution is a powerful route for controlling the oxygen sublattice evolution that affects diverse functional behavior. The controlling of the oxygen vacancy formation process is particularly important for inducing topotactic phase transitions that occur by transformation of the oxygen sublattice. Here we demonstrate an epitaxial nanocomposite approach for exploring the spatial control of topotactic phase transition from a pristine perovskite phase to an oxygen vacancy-ordered brownmillerite (BM) phase in a model oxide La 0.7 Sr 0.3 MnO 3 (LSMO). Incorporating a minority phase NiO in LSMO films creates ultrahigh density of vertically aligned epitaxial interfaces that strongly influence the oxygen vacancy formation and distribution in LSMO. Combined structural characterizations reveal strong interactions between NiO and LSMO across the epitaxial interfaces leading to a topotactic phase transition in LSMO accompanied by significant morphology evolution in NiO. Using the NiO nominal ratio as a single control parameter, we obtain intermediate topotactic nanostructures with distinct distribution of the transformed LSMO-BM phase, which enables systematic tuning of magnetic and electrical transport properties. The use of self-assembled heterostructure interfaces by the epitaxial nanocomposite platform enables more versatile design of topotactic phase structures and correlated functionalities that are sensitive to oxygen vacancies.

36 MATERIALS SCIENCE↗

Ionic Conductivity Increased by Two Orders of Magnitude in Micrometer-Thick Vertical Yttria-Stabilized ZrO 2 Nanocomposite Films

We design and create a unique cell geometry of templated micrometer-thick epitaxial nanocomposite films which contain ~20 nm diameter yttria-stabilized ZrO 2 (YSZ) nanocolumns, strain coupled to a SrTiO 3 matrix. We also enhanced the ionic conductivity of these nanocolumnsby over 2 orders of magnitude compared to plain YSZ films. Concomitant with the higher ionic conduction is the finding that the YSZ nanocolumns in the films have much higher crystallinity and orientation, compared to plain YSZ films. Hence, “oxygen migration highways” are formed in the desired out-of-plane direction. This improved structure is shown to originate from the epitaxial coupling of the YSZ nanocolumns to the SrTiO 3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO 2 nanocolumns within the SrTiO 3 matrix. Furthermore, this intermediate layer reduces the lattice mismatch between the YSZ nanocolumns and the substrate. Vertical ionic conduction values as high as 10 –2 Ω –1 cm –1 were demonstrated at 360 °C (300 °C lower than plain YSZ films), showing the strong practical potential of these nanostructured films for use in much lower operation temperature ionic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Carbon Nanotube Microarrays Grown on Nanoflake Substrates

This innovation consists of a new composition of matter where single-walled carbon nanotubes (SWNTs) are grown in aligned arrays from nanostructured flakes that are coated in Fe catalyst. This method of growth of aligned SWNTs, which can yield well over 400 percent SWNT mass per unit substrate mass, exceeds current yields for entangled SWNT growth. In addition, processing can be performed with minimal wet etching treatments, leaving aligned SWNTs with superior properties over those that exist in entangled mats. The alignment of the nanotubes is similar to that achieved in vertically aligned nanotubes, which are called "carpets. " Because these flakes are grown in a state where they are airborne in a reactor, these flakes, after growing SWNTs, are termed "flying carpets. " These flakes are created in a roll-to-roll evaporator system, where three subsequent evaporations are performed on a 100-ft (approx. =30-m) roll of Mylar. The first layer is composed of a water-soluble "release layer, " which can be a material such as NaCl. After depositing NaCl, the second layer involves 40 nm of supporting layer material . either Al2O3 or MgO. The thickness of the layer can be tuned to synthesize flakes that are larger or smaller than those obtained with a 40-nm deposition. Finally, the third layer consists of a thin Fe catalyst layer with a thickness of 0.5 nm. The thickness of this layer ultimately determines the diameter of SWNT growth, and a layer that is too thick will result in the growth of multiwalled carbon nanotubes instead of single-wall nanotubes. However, between a thickness of 0.5 nm to 1 nm, single-walled carbon nanotubes are known to be the primary constituent. After this three-layer deposition process, the Mylar is rolled through a bath of water, which allows catalyst-coated flakes to detach from the Mylar. The flakes are then collected and dried. The method described here for making such flakes is analogous to that which is used to make birefringent ink that is coated on U.S. currency. After deposition, the growth is carried out in a hot-filament chemical vapor deposition apparatus. A tungsten hot filament placed in the flow of H2 at a temperature greater than 1,600 C creates atomic hydrogen, which serves to reduce the Fe catalyst into a metallic state. The catalyst can now precipitate SWNTs in the presence of growth gases. The gases used for the experiments reported are C2H2, H2O, and H2, at rates of 2, 2, and 400 standard cubic centimeters per minute (sccm), respectively. In order to retain the flakes, a cage is constructed by spot welding stainless steel or copper mesh to form an enclosed area, in which the flakes are placed prior to growth. This allows growth gases and atomic hydrogen to reach the flakes, but does not allow the flakes, which rapidly nucleate SWNTs, to escape from the cage.

Schmidt, Howard K.↗