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Table of contents

Volume 28

Number 40, 6 October 2017

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Focus Issue Paper

404001
The following article is Open access

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Focus on unconventional lithography

A successful realisation of sub-20 nm features on silicon (Si) is becoming the focus of many technological studies, strongly influencing the future performance of modern integrated circuits. Although reactive ion etching (RIE), at both micrometric and nanometric scale has already been the target of many studies, a better understanding of the different mechanisms involved at sub-20 nm size etching is still required. In this work, we investigated the influence of the feature size on the etch rate of Si, performed by a cryogenic RIE process through cylinder-forming polystyrene-block-polymethylmethacrylate (PS-b-PMMA) diblock copolymer (DBC) masks with diameter ranging between 19–13 nm. A sensible decrease of the etch depth and etch rate was observed in the mask with the smallest feature size. For all the DBCs under investigation, we determined the process window useful for the correct transfer of the nanometric cylindrical pattern into a Si substrate. A structural and physicochemical investigation of the resulting nanostructured Si is reported in order to delineate the influence of various RIE pattern effects. Feature-size-dependent etch, or RIE-lag, is proved to significantly affect the obtained results.

Papers

Biology and medicine

405101

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Herein a novel multi-controlled drug release system for doxorubicin (DOX) was developed, in which monodisperse mesoporous Fe3O4 nanoparticles were combined with a phase change material (PCM) and polyethylene glycol 2000 (PEG2000). It is found that the PCM/PEG/DOX mixture containing 20% PEG could be dissolved into water at 42 °C. The mesoporous Fe3O4 nanoparticles prepared by the solvothermal method had sizes of around 25 nm and exhibited a mesoporous microstructure. A simple solvent evaporation process was employed to load the PCM/PEG/DOX mixture on the mesoporous Fe3O4 nanoparticles completely. In the Fe3O4@PCM/PEG/DOX system, the pores of the Fe3O4 nanoparticles were observed to be filled with the mixture of PCM/PEG/DOX. The Fe3O4@PCM/PEG/DOX system showed a saturation magnetization value of 50.0 emu g−1, lower than 71.1 emu g−1 of the mesoporous Fe3O4 nanoparticles, but it was still high enough for magnetic targeting and hyperthermia application. The evaluation on drug release performance indicated that the Fe3O4@PCM/PEG/DOX system achieved nearly zero release of DOX in vitro in body temperature, while around 80% of DOX could be released within 1.5 h at the therapeutic threshold of 42 °C or under the NIR laser irradiation for about 4 h. And a very rapid release of DOX was achieved by this system when applying an alternating magnetic field. By comparing the systems with and without PEG2000, it is revealed that the presence of PEG2000 makes DOX easy to be released from 1-tetradecanol to water, owing to its functions of increasing the solubility of DOX in 1-tetradecanol as well as decreasing the surface tension between water and 1-tetradecanol. The novel drug release system shows great potential for the development of thermo-chemotherapy of cancer treatment.

Electronics and photonics

405201

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We report the results of finite element simulations of the ON state characteristic of VO2-based threshold switching devices and compare the results with experimental data. The model is based on thermally induced threshold switching (thermal runaway) and successfully reproduces the IV characteristics showing the formation and growth of the conductive filament in the ON state. Furthermore, we compare the IV characteristics for two VO2 films with different electrical conductivities in the insulating and metallic phases as well as those based on TaOx and NbOx functional layers.

405202

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Brain-inspired neuromorphic systems have attracted much attention as new computing paradigms for power-efficient computation. Here, we report a silicon synaptic transistor with two electrically independent gates to realize a hardware-based neural network system without any switching components. The spike-timing dependent plasticity characteristics of the synaptic devices are measured and analyzed. With the help of the device model based on the measured data, the pattern recognition capability of the hardware-based spiking neural network systems is demonstrated using the modified national institute of standards and technology handwritten dataset. By comparing systems with and without inhibitory synapse part, it is confirmed that the inhibitory synapse part is an essential element in obtaining effective and high pattern classification capability.

405203

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We present matrix-free methods for fabricating highly luminescent and transparent CdSe/ZnS quantum dot (QD)/polymer nanocomposites utilizing poly(methyl methacrylate) (PMMA)-grafted QDs with various molecular weights. We found that the QD-PMMA nanocomposites prepared by these matrix-free methods were superior to those prepared by a simple blending method in relation to their optical property, QD dispersion, and quantum efficiency (QE). In particular, a matrix-free nanocomposite containing PMMA with a molecular weight of 2000 had the highest QE (52.8%) and transmittance of all the samples studied even at a very high QD concentration (49 wt%). This finding was attributed to the enhanced passivation of the QD surface due to the higher grafting density of the PMMA ligands and reduced energy transfer due to more uniform dispersion of QDs. Finally, we applied the nanocomposites to LED devices, and found that the matrix-free nanocomposite exhibited a higher color conversion efficiency and smaller redshift in the peak emission wavelength than that prepared using a simple blending method.

405204

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In this paper, we study band-to-band and intersubband (ISB) characteristics of Si- and Ge-doped GaN/AlN heterostructures (planar and nanowires) structurally designed to absorb in the short-wavelength infrared region, particularly at 1.55 μm. Regarding the band-to-band properties, we discuss the variation of the screening of the internal electric field by free carriers, as a function of the doping density and well/nanodisk size. We observe that nanowire heterostructures consistently present longer photoluminescence decay times than their planar counterparts, which supports the existence of an in-plane piezoelectric field associated to the shear component of the strain tensor in the nanowire geometry. Regarding the ISB characteristics, we report absorption covering 1.45–1.75 μm using Ge-doped quantum wells, with comparable performance to Si-doped planar heterostructures. We also report similar ISB absorption in Si- and Ge-doped nanowire heterostructures indicating that the choice of dopant is not an intrinsic barrier for observing ISB phenomena. The spectral shift of the ISB absorption as a function of the doping concentration due to many body effects confirms that Si and Ge efficiently dope GaN/AlN nanowire heterostructures.

405205

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Reducing silicon (Si) wafer thickness in the photovoltaic industry has always been demanded for lowering the overall cost. Further benefits such as short collection lengths and improved open circuit voltages can also be achieved by Si thickness reduction. However, the problem with thin films is poor light absorption. One way to decrease optical losses in photovoltaic devices is to minimize the front side reflection. This approach can be applied to front contacted ultra-thin crystalline Si solar cells to increase the light absorption. In this work, homojunction solar cells were fabricated using ultra-thin and flexible single crystal Si wafers. A metal assisted chemical etching method was used for the nanowire (NW) texturization of ultra-thin Si wafers to compensate weak light absorption. A relative improvement of 56% in the reflectivity was observed for ultra-thin Si wafers with the thickness of 20 ± 0.2 μm upon NW texturization. NW length and top contact optimization resulted in a relative enhancement of 23% ± 5% in photovoltaic conversion efficiency.

405206

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Superlattice-like Ge50Te50/Ge8Sb92 (SLL GT/GS) thin film was systematically investigated for multi-level storage and ultra-fast switching phase-change memory application. In situ resistance measurement indicates that SLL GT/GS thin film exhibits two distinct resistance steps with elevated temperature. The thermal stability of the amorphous state and intermediate state were evaluated with the Kissinger and Arrhenius plots. The phase-structure evolution revealed that the amorphous SLL GT/GS thin film crystallized into rhombohedral Sb phase first, then the rhombohedral GeTe phase. The microstructure, layered structure, and interface stability of SLL GT/GS thin film was confirmed by using transmission electron microscopy. The transition speed of crystallization and amorphization was measured by the picosecond laser pump-probe system. The volume variation during the crystallization was obtained from x-ray reflectivity. Phase-change memory (PCM) cells based on SLL GT/GS thin film were fabricated to verify the multi-level switching under an electrical pulse as short as 30 ns. These results illustrate that the SLL GT/GS thin film has great potentiality in high-density and high-speed PCM applications.

Patterning and nanofabrication

405301

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We presented surface energy-tunable nanoscale molds for unconventional lithography. The mold is highly robust, transparent, has a minimized haze, does not contain additives, and is a non-fluorinated isodecyl acrylate and trimethylolpropane triacrylate based polymer. By changing the mixing ratio of the polymer components, the cross-linking density, mechanical modulus, and surface energy (crucial factors in low pressure ((1–2) × 105 N m−2) low pressure-nanoimprint lithography (LP-NIL)), can be controlled. To verify these properties of the molds, we also characterized the surface energy by measuring the contact angles and calculating the work of adhesion among the wafer, polymer film, and mold for successful demolding in nanoscale structures. Moreover, the molds showed high optical clarity and precisely tunable mechanical and surface properties, capable of replicating sub-100 nm patterns by thermal LP-NIL and UV-NIL.

405302

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In this paper, we show that tightly focused femtosecond laser irradiation is effective in improving nanojoining of an oxide nanowire (NW) (TiO2) to a metal electrode (Pt), and how this process can be used to modify contact states. Enhanced chemical bondings are created due to localized plasmonically enhanced optical absorption at the Pt/TiO2 interface as confirmed by finite element simulations of the localized field distribution during irradiation. Nano Auger electron spectroscopy shows that the resulting heterojunction is depleted in oxygen, suggesting that a TiO2–x layer is formed between the Pt electrode and the TiO2 NW. The presence of this redox layer at the metal/oxide interface plays an important role in decreasing the Schottky barrier height and in facilitating chemical bonding. After laser irradiation at the cathode for 10 s at a fluence of 5.02 mJ cm−2, the Pt/TiO2 NW/Pt structure displays different electrical properties under forward and reverse bias voltage, respectively. The creation of this asymmetric electrical characteristic shows the way in which modification of the electronic interface by laser engineering can replace the electroforming process in resistive switching devices and how it can be used to control contact states in a metal/oxide interface.

405303

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In this work, development of semi-transparent electrodes for efficient large area organic solar cells (OSCs) has been demonstrated. Electron beam evaporated silver grids were embedded in commercially available ITO coatings on glass, through a standard negative photolithography process, in order to improve the conductivity of planar ITO substrates. The fabricated electrodes with embedded line and square patterned Ag grids reduced the sheet resistance of ITO by 25% and 40%, respectively, showing optical transmittance drops of less than 6% within the complete visible light spectrum for both patterns. Solution processed bulk heterojunction OSCs based on PTB7:[70]PCBM were fabricated on top of these electrodes with cell areas of 4.38 cm2, and the performance of these OSCs was compared to reference cells fabricated on pure ITO electrodes. The Fill Factor (FF) of the large-scale OSCs fabricated on ITO with embedded Ag grids was enhanced by 18% for the line grids pattern and 30% for the square grids pattern compared to that of the reference OSCs. The increase in the FF was directly correlated to the decrease in the series resistance of the OSCs. The maximum power conversion efficiency (PCE) of the OSCs was measured to be 4.34%, which is 23% higher than the PCE of the reference OSCs. As the presented method does not involve high temperature processing, it could be considered a general approach for development of large area organic electronics on solvent resistant, flexible substrates.

405304

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Nanoscale engineering of noble metal particles has provided numerous material configurations to selectively confine and manipulate light across the electromagnetic spectrum. Transitioning these materials to a composite form while maintaining the desired resonance properties has proven challenging. In this work, the successful integration of plasmon-focusing gold nanostars (GNSs) into polymer nanocomposites (PNCs) is demonstrated. Tailored GNSs are produced with over a 90% yield and methods to control the branching structures are shown. A protective silica capping shell is employed on the nanomaterials to facilitate survivability in the high temperate/high shear processing parameters to create optically-tuned injection molded PNCs. The developed GNS PNCs possess dichroic scattering and absorption behavior, opening up potential applications in the fields of holographic imaging, optical filtering and photovoltaics.

405305

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Strong light localization within metal nanostructures occurs by collective oscillations of plasmons in the form of electric and magnetic resonances. This so-called localized surface plasmon resonance (LSPR) has gained much interest in the development of low-cost sensing platforms in the visible spectrum. However, demonstrations of LSPR-based sensing are mostly limited to electric resonances due to the technological limitations for achieving magnetic resonances in the visible spectrum. In this work, we report the first demonstration of LSPR sensing based on fundamental magnetic resonance in the visible spectrum using ultrasmall gold v-shaped split ring resonators. Specifically, we show the ability for detecting adsorption of bovine serum albumin and cytochrome c biomolecules at monolayer levels, and the selective binding of protein A/G to immunoglobulin G.

Energy at the nanoscale

405401
The following article is Free article

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Biomass lignin, as a significant renewable resource, is one of the most abundant natural polymers in the world. Here, we report a novel silicon-based material, in which lignin-derived functional conformal network crosslinks the silicon nanoparticles via self-assembly. This newly-developed material could greatly solve the problems of large volume change during lithiation/delithiation process and the formation of unstable solid electrolyte interphase layers on the silicon surface. With this anode, the battery demonstrates a high capacity of ∼3000 mA h g−1, a highly stable cycling retention (∼89% after 100 cycles at 300 mA g−1) and an excellent rate capability (∼800 mA h g−1 at 9 A g−1). Moreover, the feasibility of full lithium-ion batteries with the novel silicon-based material would provide wide range of applications in the field of flexible energy storage systems for wearable electronic devices.

Sensing and actuating

405501

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We have studied the fabrication of highly efficient glucose sensors using well-ordered heterogeneous ZnO/ZnS core/shell nanotube arrays (CSNAs). The modified electrodes exhibit a superior electrochemical response towards ferrocyanide/ferricyanide and in glucose sensing. Further, the fabricated glucose biosensor exhibited good performance over an acceptable linear range from 2.39 × 10−5 to 2.66 × 10−4 mM, with a sensitivity of 188.34 mA mM−1 cm−2, which is higher than that of the ZnO nanotube array counterpart. A low limit of detection was realized (24 μM), which is good compared with electrodes based on conventional structures. In addition, the enhanced direct electrochemistry of glucose oxidase indicates the fast electron transfer of ZnO/ZnS CSNA electrodes, with a heterogeneous electron transfer rate constant (Ks) of 1.69 s−1. The fast electron transfer is attributed to the high conductivity of the modified electrodes. The presented ZnS shell can facilitate the construction of future sensors and enhance the ZnO surface in a biological environment.

405502

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Uniform Au nanoparticle (NP)/poly (acrylamide-co-acrylic acid) [P(AAm-co-AA)] hydrogel microbeads were successfully prepared using droplet microfluidics technology. The microbeads exhibited a good stimuli-responsive behavior to pH value. Particularly in the pH value ranging from pH 2–pH 9, the composite microbead sizes gradually increased along with the increase of pH value. The homogeneous Au NPs, which were encapsulated in the P(AAm-co-AA) hydrogel microbeads, could transform the volume changes of hydrogel into optical signals by a tested single microbead with a microspectrometre system. The glucose was translated into gluconic acid by glucose oxidase. Thus, the Au NP/P(AAm-co-AA) hydrogel microbeads were used for detecting glucose based on pH effects on the composite microbeads. For this, the single Au NP/P(AAm-co-AA) hydrogel microbead could act as a good pH- or glucose-visualizing sensor.

Materials: synthesis or self-assembly

405601

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We present the design of multicompartment metal oxide/silica nanofibrous photocatalysts by colloid-electrospinning and subsequent calcination. During the calcination process, silica nanomaterials are cemented to form the fibrous framework and metal oxide precursors are crystallized inside and onto the fibers. This multicompartment nanofibrous structure, constructed with nanoparticles and core–shell nanocapsules, is therefore beneficial for the separation of the materials and the light utilization due to the multiple reflections and scattering of incident light in the cavities. The photocatalytic activity of the fibers was verified by the successful degradation of a model dye rhodamine B. This synthetic methodology is a universal approach for the fabrication of nanomaterials with hierarchical hollow structures, which are emerging in energy and environmental related applications.

405602

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The technology of surface-enhanced Raman scattering (SERS) has found many applications and may find more if it can possess both sensitivity and thermal stability. This paper reports a rational design of Ag nanorods to simultaneously achieve two competing goals: the sensitivity and the thermal stability of SERS substrates. The Ag nanorods are designed and synthesized using physical vapor deposition under the condition of glancing angle incidence. The working pressure of the vacuum chamber is controlled so the mean free path of depositing atoms is comparable to the dimension of the chamber, so as to grow Ag nanorods with small diameter, and small but clear separation for optimal SERS sensitivity. Such Ag nanorods are further capped with Al2O3 on their top surfaces to reduce the diffusion-induced coarsening at high temperatures, and thereby to improve the thermal stability for SERS detections. Meanwhile, since the side surfaces of Ag nanorods are not coated with oxides in this approach, the SERS sensitivity is largely preserved while good thermal stability is achieved.

405603

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The amorphous to anatase transformation of anodized nanotubular titania surfaces has been studied by x-ray diffraction and transmission electron microscopy (TEM). A more rapid heat treatment for conversion of amorphous to crystalline anatase favorable for orthopedic implant applications was demonstrated. Nanotube titania surfaces were fabricated by electrochemical anodization of Ti6Al4V in an electrolyte containing 0.2 wt% NH4F, 60% ethylene glycol and 40% deionized water. The resulting surfaces were systematically heat treated in air with isochronal and isothermal experiments to study the temperature and time dependent transformation respectively. Energy dispersive spectroscopy shows that the anatase phase transformation of TiO2 in the as-anodized amorphous nanotube layer can be achieved in as little as 5 min at 350 °C in contrast to reports of higher temperature and much longer time. Crystallinity analysis at different temperatures and times yield transformation rate coefficients and activation energy for crystalline anatase coalescence. TEM confirms the (101) TiO2 presence within the nanotubes. These results confirm that for applications where amorphous titania nanotube surfaces are converted to crystalline anatase, a 5 min production flow-through heating process could be used instead of a 3 h batch process, reducing time, cost, and complexity.

Materials: properties, characterization or tools

405701

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The piezoelectric response, conductivity and surface potential of individual grains and grain boundaries in free-standing polycrystalline ZnO nano- and microstructured platelets is studied using scanning probe based techniques on the nanoscale. We find that applied dc electric fields can alter the piezoresponse in individual grains, as well as the local nanoscale conductivity, and invert the relative surface potential at grain boundaries. This can be attributed to defect accumulation at the grain surfaces and at grain boundaries and the associated density of carriers. Together with recently observed below-bandgap photoconductivity at grain boundaries, the presented observation opens new venues for potential nanoelectronic applications that rely on grain and grain boundary engineering and functionality in a wide-bandgap transparent material.

405702

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We fabricated synthetic double-crossover (DX) DNA lattices and natural salmon DNA (SDNA) thin films, doped with 3 combinations of double divalent metal ions (M2+)-doped groups (Co2+–Ni2+, Cu2+–Co2+, and Cu2+–Ni2+) and single combination of a triple M2+-doped group (Cu2+–Ni2+–Co2+) at various concentrations of M2+ ([M2+]). We evaluated the optimum concentration of M2+ ([M2+]O) (the phase of M2+-doped DX DNA lattices changed from crystalline (up to ([M2+]O) to amorphous (above [M2+]O)) and measured the current, absorbance, and photoluminescent characteristics of multiple M2+-doped SDNA thin films. Phase transitions (visualized in phase diagrams theoretically as well as experimentally) from crystalline to amorphous for double (Co2+–Ni2+, Cu2+–Co2+, and Cu2+–Ni2+) and triple (Cu2+–Ni2+–Co2+) dopings occurred between 0.8 mM and 1.0 mM of Ni2+ at a fixed 0.5 mM of Co2+, between 0.6 mM and 0.8 mM of Co2+ at a fixed 3.0 mM of Cu2+, between 0.6 mM and 0.8 mM of Ni2+ at a fixed 3.0 mM of Cu2+, and between 0.6 mM and 0.8 mM of Co2+ at fixed 2.0 mM of Cu2+ and 0.8 mM of Ni2+, respectively. The overall behavior of the current and photoluminescence showed increments as increasing [M2+] up to [M2+]O, then decrements with further increasing [M2+]. On the other hand, absorbance at 260 nm showed the opposite behavior. Multiple M2+-doped DNA thin films can be used in specific devices and sensors with enhanced optoelectric characteristics and tunable multi-functionalities.

405703

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We report the fabrication and physical characteristics of niobium ion (Nb5+)-doped double-crossover DNA (DX-DNA) and salmon DNA (SDNA) thin films. Different concentrations of Nb5+ ([Nb5+]) are coordinated into the DNA molecules, and the thin films are fabricated via substrate-assisted growth (DX-DNA) and drop-casting (SDNA) on oxygen plasma treated substrates. We conducted atomic force microscopy to estimate the optimum concentration of Nb5+ ([Nb5+]O = 0.08 mM) in Nb5+-doped DX-DNA thin films, up to which the DX-DNA lattices maintain their structures without deformation. X-ray photoelectron spectroscopy (XPS) was performed to probe the chemical nature of the intercalated Nb5+ in the SDNA thin films. The change in peak intensities and the shift in binding energy were witnessed in XPS spectra to explicate the binding and charge transfer mechanisms between Nb5+ and SDNA molecules. UV-visible, Raman, and photoluminescence (PL) spectra were measured to determine the optical properties and thus investigate the binding modes, Nb5+ coordination sites in Nb5+-doped SDNA thin films, and energy transfer mechanisms, respectively. As [Nb5+] increases, the absorbance peak intensities monotonically increase until ∼[Nb5+]O and then decrease. However, from the Raman measurements, the peak intensities gradually decrease with an increase in [Nb5+] to reveal the binding mechanism and binding sites of metal ions in the SDNA molecules. From the PL, we observe the emission intensities to reduce them at up to ∼[Nb5+]O and then increase after that, expecting the energy transfer between the Nb5+ and SDNA molecules. The current–voltage measurement shows a significant increase in the current observed as [Nb5+] increases in the SDNA thin films when compared to that of pristine SDNA thin films. Finally, we investigate the temperature dependent magnetization in which the Nb5+-doped SDNA thin films reveal weak ferromagnetism due to the existence of tiny magnetic dipoles in the Nb5+-doped SDNA complex.

405704

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Developing a thermally stable nanofluid that can maintain good thermo-conductive and flow performance at moderate or elevated temperatures for prolonged periods of time is a great challenge in heat transfer applications. Here, the thermal conductivity and rheological properties as well as their thermal stability characteristics of a nanofluid containing two-dimensional (2D) hexagonal boron nitride nanosheets (h-BNNSs) in ethylene glycol (EG) are presented, in comparison with those for a graphene oxide (GO) nanofluid as a counterpart. In place of a surfactant, hydroxyl functional groups covalently bound to the BNNS surface provided excellent compatibility and stable dispersion of the particles within EG at temperatures up to 90 °C. Owing to the percolation effect of the 2D sheets, the thermal conductivity of the EG base fluid was significantly enhanced by 80% at 5 vol% of BNNS, superior to that of the GO fluid. Moreover, the BNNS fluids exhibited excellent long-term stability at 90 °C for 5 d without loss of their high thermal conductivity, low viscosity and electrical insulating property, whereas the GO fluids underwent thermal degradation with irreversible particle aggregation and increasing viscosity due to the selective chemical reduction of the surface functional groups (i.e., C–O groups) of the GO.

405705

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The effect of the oxidation of gallium nanoparticles (Ga NPs) on their plasmonic properties is investigated. Discrete dipole approximation has been used to study the wavelength of the out-of-plane localized surface plasmon resonance in hemispherical Ga NPs, deposited on silicon substrates, with oxide shell (Ga2O3) of different thickness. Thermal oxidation treatments, varying temperature and time, were carried out in order to increase experimentally the Ga2O3 shell thickness in the NPs. The optical, structural and chemical properties of the oxidized NPs have been studied by spectroscopic ellipsometry, scanning electron microscopy, grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. A clear redshift of the peak wavelength is observed, barely affecting the intensity of the plasmon resonance. A controllable increase of the Ga2O3 thickness as a consequence of the thermal annealing is achieved. In addition, simulations together with ellipsometry results have been used to determine the oxidation rate, whose kinetics is governed by a logarithmic dependence. These results support the tunable properties of the plasmon resonance wavelength in Ga NPs by thermal oxidation at low temperatures without significant reduction of the plasmon resonance intensity.

405706

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Hierarchically structured nanomaterials play an important role in both light absorption and separation of photo-generated charges. In the present study, hierarchically branched TiO2 nanostructures (HB-MLNTs) are obtained through hydrothermal transformation of electrochemically anodized TiO2 multi-leg nanotubes (MLNT) arrays. Photo-anodes based on HB-MLNTs demonstrated 5 fold increase in applied bias to photo-conversion efficiency (%ABPE) over that of TiO2 MLNTs without branches. Further, such nanostructures are wrapped with reduced graphene oxide (rGO) films to enhance the charge separation, which resulted in ∼6.5 times enhancement in %ABPE over that of bare MLNTs. We estimated charge transport (ηtr) and charge transfer (ηct) efficiencies by analyzing the photo-current data. The ultra-fine nano branches grown on the MLNTs are effective in increasing light absorption through multiple scattering and improving charge transport/transfer efficiencies by enlarging semiconductor/electrolyte interface area. The charge transfer resistance, interfacial capacitance and electron decay time have been estimated through electrochemical impedance measurements which correlate with the results obtained from photocurrent measurements.