Multiresonant plasmon excitation in slit antennas on metallic and hyperbolic metamaterials.

A comparative study of the optical properties of random and ordered arrays of metallic and hyperbolic slit antennas is presented. The metallic slits are fabricated on Au layers, whereas the hyperbolic ones are fabricated on Au/MgO multilayers. The random arrays show, for both types of antennas, similar slit plasmon resonances whose positions depend on the internal structure of the supporting layer. On the other hand, the spectra of the ordered arrays of the hyperbolic slits present additional resonances related to the excitation of Bloch plasmon polaritons in the hyperbolic layer. By varying the slit length and periodicity, an analysis of the interaction between slit localized resonance and Bloch plasmon polaritons is also presented.

Pulsed current-voltage electrodeposition of stoichiometric Bi2Te3 nanowires and their crystallographic characterization by transmission electron backscatter diffraction.

Bi2Te3 nanowires with diameters ranging from 25 to 270 nm, ultra-high aspect ratio, and uniform growth front were fabricated by electrodeposition, pulsing between zero current density during the off time and constant potential during the on time (pulsed-current-voltage method, p-IV). The use of zero current density during the off time is to ensure no electrodeposition is carried out and the system is totally relaxed. By this procedure, stoichiometric nanowires oriented perpendicular to the c-axis is obtained for the different diameters of porous alumina templates. In addition, the samples show a uniform growth front with ultra-high aspect ratio single crystal nanowires. The high degree of crystallinity was verified by transmission electron backscatter diffraction. This characterization revealed that the nanowires present both large single crystalline areas and areas with alternating twin configurations.

The fingerprint of Te-rich and stoichiometric Bi2Te3 nanowires by Raman spectroscopy.

We unambiguously show that the signature of Te-rich bismuth telluride is the appearance of three new peaks in the Raman spectra of Bi2Te3, located at 88, 117 and 137 cm(-1). For this purpose, we have grown stoichiometric Bi2Te3 nanowires as well as Te-rich nanowires. The absence of these peaks in stoichiometric nanowires, even in those with the smallest diameter, shows that they are not related to confinement effects or the lack of inversion symmetry, as stated in the literature, but to the existence of Te clusters. These Te clusters have been found in non-stoichiometric samples by high resolution electron microscopy, while they are absent in stoichiometric samples. The Raman spectra of the latter corresponds to the one for bulk Bi2Te3. The intensity of these Raman peaks are clearly correlated to the Te content. In order to ensure statistically meaningful results, we have investigated several regions from every sample.

Fabrication and mechanical characterization of semi-free-standing (conjugated) polymer thin films.

Polymers undergo severe low-dimensionality effects when they are confined to ultrathin films since most of the structural and dynamical processes involving polymer molecules are correlated to length scales of the order of nanometers. However, the real influence of the size limitation over such processes is often hard to identify as it is masked by interfacial effects. We present the fabrication of a new type of nanostructure consisting of poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl] (PCDTBT) thin film that is held up exclusively over tips of poly(ether-ether-ketone) (PEEK) nanopillars. The fabrication method exploits the nonwetting behavior of PCDTBT onto an ordered PEEK nanopillar array when the mobility of the PCDTBT molecules is enhanced by a solvent annealing process. We use this new configuration to characterize the mechanical behavior of free-standing thin film regions, thus in the absence of underlaying substrate, by means of an atomic force microscope (AFM) setup. First, we study how the finite thickness and/or the presence of the underlying substrate influences the mechanical modulus of the material in the linear elastic regime. Moreover, we analyze deep indentations up to the rupture of the thin film, which allow for the measurement of important mechanical features of the nanoconfined polymer, such as its yield strain, the rupture strain, the bending rigidity, etc., which are impossible to investigate in thin films deposited on substrates.

Poly(3-hexylthiophene) nanowires in porous alumina: internal structure under confinement.

We study the structure of poly(3-hexylthiophene) (P3HT) subjected to nanoscale confinement in two dimensions (2D) as imposed by the rigid walls of nanopore anodic aluminum oxide (AAO) templates. P3HT nanowires with aspect ratios (length-to-diameter) above 1000 and diameters ranging between 15 nm and 350 nm are produced in the pores of the AAO templates via two processing routes. These are, namely, drying a solution or cooling from the melt. Our study focuses on the effects of nanoconfinement on the semicrystalline nature of the nanowires, the orientation of crystals, and the evolution of the structures that P3HT might develop under confinement, which we investigate by combining imaging (SEM), spectroscopic (FTIR, photoluminescence) and structural characterization (WAXS, DSC) techniques. Solution-processed P3HT nanowires are essentially amorphous and porous, whereas melt-processed nanowires are semicrystalline, and present a more compact morphology and smoother surfaces. In the latter case, the orientation of crystals was found to strongly depend on the pore diameter. In large diameter nanowires (250 nm and 120 nm), crystals are oriented laying the π-π stacking direction parallel to the nanowire axis. In contrast, in small diameter nanowires, the π-π stacking direction is mainly perpendicular to the nanowires, as crystals are likely to nucleate at pore walls. The structural evolution of P3HT upon heating into weakly (250 nm in diameter) and strongly (15 nm in diameter) confining pores has been studied. A complex set of structures is observed, i.e., crystals, a solid layered mesophase, a nematic/smectic mesophase, and the isotropic melt. Interestingly, a rare crystal polymorph (form II) is also observed under strong confinement conditions together with the usual lamellar crystal form I. Furthermore, we show that nanoconfinement stabilizes form II: such crystals are still present at 210 °C while in the bulk they get converted to form I crystals at around 50 °C.

Suitability of Anodic Porous Alumina as a Passive Radiative Cooler: An In-Depth Study.

Passive radiative cooling technology has the potential to revolutionize the way of cooling buildings and devices, while also helping to reduce the carbon footprint and energy consumption. Pioneer works involving anodic aluminum oxide (AAO) nanostructures showed controversial results. In this work, we clarify how the morphological properties and chemical structure of AAO-Al samples affect their optical properties and their cooling performance. Changes in thickness, interpore distance, and porosity of the alumina layer, as well as the used counterions, significantly affect the cooling ability of the AAO-Al structure. We measure a maximum temperature reduction, ΔT, of 8.0 °C under direct sunlight on a summer day in Spain, coinciding with a calculated peak cooling power, P cool, of 175 W/m2, using an AAO-Al sample anodized in sulfuric acid, with 12 µm of AAO thickness and 10% of porosity. These results represent a significant improvement over previous studies, demonstrating the potential of AAO nanostructures to be used in thermal management applications.

Sputtering Codeposition and Metal-Induced Crystallization to Enhance the Power Factor of Nanocrystalline Silicon.

The power factor of highly boron-doped nanocrystalline Si thin films with controlled doping concentration is investigated. We achieve a high degree of tuning of boron content with a charge carrier concentration from 1018 to 1021/cm3 and with the electrical conductivity by varying the boron magnetron power from 10 to 60 W while maintaining the power of a SiB source constant during codeposition from two independent sputtering sources. Along with the increase in the electrical conductivity with increased boron doping, we observe a steady decrease in the Seebeck coefficient from 500 to 100 µV/K. These values result in power factors that exhibit a marked maximum of 5 mW/K2m for a carrier concentration of around 1021/cm3 at room temperature. Temperature-dependent measurements up to 650 °C show, with increasing doping concentration, a change of the resistivity from a semiconducting to a metallic behavior and an increase of both Seebeck coefficient and power factor, with this last one peaking at 9.8 mW/K2m in the 350-550 °C temperature range. For higher concentrations, scanning electron microscopy and energy-dispersive X-ray spectroscopy show a partial segregation of boron on particles on the surface. These results exemplify the great advantage of sputtering codeposition methods to easily tune and optimize the thermoelectric performance in thin films, obtaining in our specific case highly competitive power factors in a simple and reliable manner.

Localization and Directionality of Surface Transport in Bi2Te3 Ordered 3D Nanonetworks.

The resistance of an ordered 3D-Bi2Te3 nanowire nanonetwork was studied at low temperatures. Below 50 K the increase in resistance was found to be compatible with the Anderson model for localization, considering that conduction takes place in individual parallel channels across the whole sample. Angle-dependent magnetoresistance measurements showed a distinctive weak antilocalization characteristic with a double feature that we could associate with transport along two perpendicular directions, dictated by the spatial arrangement of the nanowires. The coherence length obtained from the Hikami-Larkin-Nagaoka model was about 700 nm across transversal nanowires, which corresponded to approximately 10 nanowire junctions. Along the individual nanowires, the coherence length was greatly reduced to about 100 nm. The observed localization effects could be the reason for the enhancement of the Seebeck coefficient observed in the 3D-Bi2Te3 nanowire nanonetwork compared to individual nanowires.

Ordered arrays of polymeric nanopores by using inverse nanostructured PTFE surfaces.

We present a simple, efficient, and high-throughput methodology for the fabrication of ordered nanoporous polymeric surfaces with areas in the range of cm(2). The procedure is based on a two-stage replication of a master nanostructured pattern. The process starts with the preparation of an ordered array of poly(tetrafluoroethylene) (PTFE) free-standing nanopillars by wetting self-ordered porous anodic aluminum oxide templates with molten PTFE. The nanopillars are 120 nm in diameter and approximately 350 nm long, while the array extends over cm(2). The PTFE nanostructuring process induces surface hydrocarbonation of the nanopillars, as revealed by confocal Raman microscopy/spectroscopy, which enhances the wettability of the originally hydrophobic material and facilitates its subsequent use as an inverse pattern. Thus, the PTFE nanostructure is then used as a negative master for the fabrication of macroscopic hexagonal arrays of nanopores composed of biocompatible poly(vinylalcohol). In this particular case, the nanopores are 130-140 nm in diameter and the interpore distance is around 430 nm. Features of such characteristic dimensions are known to be easily recognized by living cells. Moreover, the inverse mold is not destroyed in the pore array demolding process and can be reused for further pore array fabrication. Therefore, the developed method allows the high-throughput production of cm(2)-scale biocompatible nanoporous surfaces that could be interesting as two-dimensional scaffolds for tissue repair or wound healing. Moreover, our approach can be extrapolated to the fabrication of almost any polymer and biopolymer ordered pore array.

Plasmon Resonances in 1D Nanowire Arrays and 3D Nanowire Networks of Topological Insulators and Metals.

The 1D nanowire arrays and 3D nanowire networks of topological insulators and metals have been fabricated by template-assisted deposition of Bi2Te3 and Ni inside anodic aluminum oxide (AAO) templates, respectively. Despite the different origins of the plasmon capabilities of the two materials, the results indicate that the optical response is determined by plasmon resonances, whose position depends on the nanowire interactions and material properties. Due to the thermoelectric properties of Bi2Te3 nanowires, these plasmon resonances could be used to develop new ways of enhancing thermal gradients and their associated thermoelectric power.

The Thermoelectric Properties of Spongy PEDOT Films and 3D-Nanonetworks by Electropolymerization.

Recently, polymers have been attracted great attention because of their thermoelectric materials' excellent mechanical properties, specifically their cost-effectiveness and scalability at the industrial level. In this study, the electropolymerization conditions (applied potential and deposition time) of PEDOT films were investigated to improve their thermoelectric properties. The morphology and Raman spectroscopy of the PEDOT films were analyzed according to their applied potential and deposition time. The best thermoelectric properties were found in films grown at 1.3 V for 10 min, with an electrical conductivity of 158 ± 8 S/cm, a Seebeck coefficient of 33 ± 1 µV/K, and a power factor of 17 ± 2 µW/K·m2. This power factor value is three times higher than the value reported in the literature for electropolymerized PEDOT films in acetonitrile using lithium perchlorate as a counter-ion. The thermal conductivity was found to be (1.3 ± 0.3) × 10-1 W/m·K. The highest figure of merit obtained at room temperature was (3.9 ± 1.0) × 10-2 using lithium perchlorate as a counter-ion. In addition, three-dimensional (3D) PEDOT nanonetworks were electropolymerized inside 3D anodic aluminum oxide (3D AAO), obtaining lower values in their thermoelectric properties.

Nanoscale heat transport analysis by scanning thermal microscopy: from calibration to high-resolution measurements.

Scanning thermal microscopy (SThM) is a powerful technique for thermal characterization. However, one of the most challenging aspects of thermal characterization is obtaining quantitative information on thermal conductivity with nanoscale lateral resolution. We used this technique with the cross-point calibration method to obtain the thermal contact resistance, R c, and thermal exchange radius, b, using thermo-resistive Pd/Si3N4 probes. The cross-point curves correlate the dependence of R c and b with the sample's thermal conductivity. We implemented a 3ω-SThM method in which reference samples with known thermal conductivity were used in the calibration and validation process to guarantee optimal working conditions. We achieved values of R c = 0.94 × 106 ± 0.02 K W-1 and b = 2.41 × 10-7 ± 0.02 m for samples with a low thermal conductivity (between 0.19 and 1.48 W m-1 K-1). These results show a large improvement in spatial resolution over previously reported data for the Wollaston probes (where b ∼ 2.8 µm). Furthermore, the contact resistance with the Pd/Si3N4 is ∼20× larger than reported for a Wollaston wire probe (with 0.45 × 105 K W-1). These thermal parameters were used to determine the unknown thermal conductivity of thermoelectric films of Ag2Se, Ag2-x Se, Cu2Se (smooth vs. rough surface), and Bi2Te3, obtaining, in units of W m-1 K-1, the values of 0.63 ± 0.07, 0.69 ± 0.15, 0.79 ± 0.03, 0.82 ± 0.04, and 0.93 ± 0.12, respectively. To the best of our knowledge, this is the first time these microfabricated probes have been calibrated using the cross-point method to perform quantitative thermal analysis with nanoscale resolution. Moreover, this work shows high-resolution thermal images of the V 1ω and V 3ω signals, which can offer relevant information on the material's heat dissipation.

Tunable Carrier Type of a Semiconducting 2D Metal-Organic Framework Cu3(HHTP)2.

In this work, a switch from n-type to p-type conductivity in electrodeposited Cu3(2,3,6,7,10,11-hexahydroxytriphenylene)2 [Cu3(HHTP2)] has been observed, which is most likely due to oxygen molecular doping. The synthesis of electrically conductive 2D metal-organic frameworks (MOFs) has been achieved through the introduction of highly conjugated organic linkers coordinated to their constituent metal-ion centers. However, the porous structure and unsaturated metal sites in MOFs make them susceptible to ambient adsorbates, which can affect their charge transport properties. This phenomenon has been experimentally investigated by GIXRD, Hall effect and Seebeck measurements, and X-ray photoelectron spectroscopy.

Effects of nanostructuration on the electrochemical performance of metallic bioelectrodes.

The use of metallic nanostructures in the fabrication of bioelectrodes (e.g., neural implants) is gaining attention nowadays. Nanostructures provide increased surface area that might benefit the performance of bioelectrodes. However, there is a need for comprehensive studies that assess electrochemical performance of nanostructured surfaces in physiological and relevant working conditions. Here, we introduce a versatile scalable fabrication method based on magnetron sputtering to develop analogous metallic nanocolumnar structures (NCs) and thin films (TFs) from Ti, Au, and Pt. We show that NCs contribute significantly to reduce the impedance of metallic surfaces. Charge storage capacity of Pt NCs is remarkably higher than that of Pt TFs and that of the other metals in both morphologies. Circuit simulations of the electrode/electrolyte interface show that the signal delivered in voltage-controlled systems is less filtered when nanocolumns are used. In a current-controlled system, simulation shows that NCs provide safer stimulation conditions compared to TFs. We have assessed the durability of NCs and TFs for potential use in vivo by reactive accelerated aging test, mimicking one-year in vivo implantation. Although each metal/morphology reveals a unique response to aging, NCs show overall more stable electrochemical properties compared to TFs in spite of their porous structure.

Revisiting anodic alumina templates: from fabrication to applications.

Anodic porous alumina, -AAO- (also known as nanoporous alumina, nanohole alumina arrays, -NAA- or nanoporous anodized alumina platforms, -NAAP-) has opened new opportunities in a wide range of fields, and is used as an advanced photonic structure for applications in structural coloration and advanced optical biosensing based on the ordered nanoporous structure obtained and as a template to grow nanowires or nanotubes of different materials giving rise to metamaterials with tailored properties. Therefore, understanding the structure of nanoporous anodic alumina templates and knowing how they are fabricated provide a tool for the further design of structures based on them, such as 3D nanoporous structures developed recently. In this work, we review the latest developments related to nanoporous alumina, which is currently a very active field, to provide a solid and thorough reference for all interested experts, both in academia and industry, on these nanostructured and highly useful structures. We present an overview of theories on the formation of pores and self-ordering in alumina, paying special attention to those presented in recent years, and different nanostructures that have been developed recently. Therefore, a wide variety of architectures, ranging from ordered nanoporous structures to diameter changing pores, branched pores, and 3D nanostructures will be discussed. Next, some of the most relevant results using different nanostructured morphologies as templates for the growth of different materials with novel properties and reduced dimensionality in magnetism, thermoelectricity, etc. will be summarised, showing how these structures have influenced the state of the art in a wide variety of fields. Finally, a review on how these anodic aluminium membranes are used as platforms for different applications combined with optical techniques, together with principles behind these applications will be presented, in addition to a hint on the future applications of these versatile nanomaterials. In summary, this review is focused on the most recent developments, without neglecting the basis and older studies that have led the way to these findings. Thus, it gives an updated state-of-the-art review that should be useful not only for experts in the field, but also for non-specialists, helping them to gain a broad understanding of the importance of anodic porous alumina, and most probably, endow them with new ideas for its use in fields of interest or even developing the anodization technique.

3D Bi2Te3 Interconnected Nanowire Networks to Increase Thermoelectric Efficiency.

3D interconnected nanowire scaffoldings are shown to increase the thermoelectric efficiency in comparison to similar diameter 1D nanowires and films grown under similar electrodeposition conditions. Bi2Te3 3D nanonetworks offer a reduction in thermal conductivity (κT) while preserving the high electrical conductivity of the films. The reduction in κT is modeled using the hydrodynamic heat transport equation, and it can be understood as a heat viscosity effect due to the 3D nanostructuration. In addition, the Seebeck coefficient is twice that of nanowires and films, and up to 50% higher than in a single crystal. This increase is interpreted as a nonequilibrium effect that the geometry of the structure induces on the distribution function of the phonons, producing an enhanced phonon drag. These thermoelectric metamaterials have higher performance and are fabricated with large areas by a cost-effective method, which makes them suitable for up-scale production.

Electrodeposition of V-VI Nanowires and Their Thermoelectric Properties.

Nanostructuration is an intensive field of research due to the appearance of interesting properties at the nanoscale. For instance, in thermoelectricity the most outstanding improvements obtained lately are related to phenomena that appear as a result of nano-engineering different materials. The thermoelectric effect is the direct conversion from temperature gradients into electricity and vice versa. When going to low dimensions, for example in the particular case of thermoelectric nanowires, the transport properties of phonons are modified with respect to those found in bulk leading to a higher thermoelectric figure of merit z. In more detail, this review tries to compile some of the landmarks in the electrodeposition of Bi2Te3-based nanowires. We will focus on the achievements using different templates, electrolytes and deposition modes. We will also summarize the measurements performed in those nanowires and the main conclusions that can be extracted from the published works. Finally, an update of nanowire-based thermoelectric generators is also included.

Highly Efficient Antimicrobial Ceramics Based on Electrically Charged Interfaces.

The increasing threat of multidrug-resistant microorganisms is a cause of worldwide concern. This motivates a necessity to discover new antimicrobial agents or new mechanisms for microorganism eradication, different from those currently used. Here, we report an effective antibacterial ceramic glaze that combines different bactericidal mechanisms. Specifically, the used methodology of the glaze results in glass-free edge crystallizations of feldspar structures at the ceramic surface. A combination of Rutherford backscattering spectroscopy, scanning electron microscopy, and Raman microscopy is used to determine the chemical elements and crystallizations at the ceramic surface. Moreover, Kelvin probe force microscopy demonstrates that the presence of glass-free edges in feldspar needle crystals (semiconductor phase) on a glass matrix (insulator phase) promotes the formation of semiconductor-insulator interface barriers. These barriers act as reservoirs of electric charges of ∼1.5 V, producing a discharge exceeding the microorganism membrane breakdown value (up to 0.5 V). Furthermore, the surface crystallizations account for the formation of a microroughness that limits biofilm formation. Both factors result in high antibacterial activity in the range of R > 4 for Escherichia coli and Staphylococcus aureus. This approach opens new possibilities to attain bactericidal surfaces and to understand the role of physical interaction as a main antimicrobial mechanism.

Three-Dimensional Bi2Te3 Networks of Interconnected Nanowires: Synthesis and Optimization.

Self-standing Bi2Te3 networks of interconnected nanowires were fabricated in three-dimensional porous anodic alumina templates (3D⁻AAO) with a porous structure spreading in all three spatial dimensions. Pulsed electrodeposition parameters were optimized to grow highly oriented Bi2Te3 interconnected nanowires with stoichiometric composition inside those 3D⁻AAO templates. The nanowire networks were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and Raman spectroscopy. The results are compared to those obtained in films and 1D nanowires grown under similar conditions. The crystalline structure and composition of the 3D Bi⁻Te nanowire network are finely tuned by controlling the applied voltage and the relaxation time off at zero current density during the deposition. With this fabrication method, and controlling the electrodeposition parameters, stoichiometric Bi2Te3 networks of interconnected nanowires have been obtained, with a preferential orientation along [1 1 0], which makes them optimal candidates for out-of-plane thermoelectric applications. Moreover, the templates in which they are grown can be dissolved and the network of interconnected nanowires is self-standing without affecting its composition and orientation properties.

Exploring New Mechanisms for Effective Antimicrobial Materials: Electric Contact-Killing Based on Multiple Schottky Barriers.

The increasing threat of multidrug-resistance organisms is a cause for worldwide concern. Progressively microorganisms become resistant to commonly used antibiotics, which are a healthcare challenge. Thus, the discovery of new antimicrobial agents or new mechanisms different from those used is necessary. Here, we report an effective and selective antimicrobial activity of microstructured ZnO (Ms-ZnO) agent through the design of a novel star-shaped morphology, resulting in modulation of surface charge orientation. Specifically, we find that Ms-ZnO particles are composed of platelet stacked structure, which generates multiple Schottky barriers due to the misalignment of crystallographic orientations. We also demonstrated that this effect allows negative charge accumulation in localized regions of the structure to act as "charged domain walls", thereby improving the antimicrobial effectiveness by electric discharging effect. We use a combination of field emission scanning electron microscopy (FE-SEM), SEM-cathodoluminescence imaging, and Kelvin probe force microscopy (KPFM) to determine that the antimicrobial activity is a result of microbial membrane physical damage caused by direct contact with the Ms-ZnO agent. It is important to point out that Ms-ZnO does not use the photocatalysis or the Zn2+ released as the main antimicrobial mechanism, so consequently this material would show low toxicity and robust stability. This approach opens new possibilities to understand both the physical interactions role as main antimicrobial mechanisms and insight into the coupled role of hierarchical morphologies and surface functionality on the antimicrobial activity.