Semiconductor-like Sensitivity in Metallic Ultrathin Gold Nanowire-Based Sensors

Due to the ease of modification of electronic structure upon analyte adsorption, semiconductors have been the preferred materials as chemical sensors. At reduced dimension, however, the sensitivity of semiconductor-based sensors deteriorates significantly due to passivation, and often by increased band gap caused by quantum confinement. Using first-principles density functional theory combined with Boltzmann transport calculations, we demonstrate semiconductor-like sensitivity toward chemical species in ultrathin gold nanowires (AuNWs). The sensing mechanism is governed by the modification of the electronic structure of the AuNW as well as scattering of the charge carriers by analyte adsorption. Most importantly, the sensitivity exhibits a linear relationship with the electron affinities of the respective analytes. Based on this relationship, we propose an empirical parameter, which can predict an analyte-specific sensitivity of a AuNW, rendering them as effective sensors for a wide range of chemical an alytes.

Wrinkling of Atomic Planes in Ultrathin Au Nanowires

A detailed understanding of structure and stability of nanowires is critical for applications. Atomic resolution imaging of ultrathin single crystalline Au nanowires using aberration-corrected microscopy reveals an intriguing relaxation whereby the atoms in the close-packed atomic planes normal to the growth direction are displaced in the axial direction leading to wrinkling of the (111) atomic plane normal to the wire axis. First-principles calculations of the structure of such nanowires confirm this wrinkling phenomenon, whereby the close-packed planes relax to form saddle-like surfaces. Molecular dynamics studies of wires with varying diameters and different bounding surfaces point to the key role of surface stress on the relaxation process. Using continuum mechanics arguments, we show that the wrinkling arises due to anisotropy in the surface stresses and in the elastic response, along with the divergence of surface-induced bulk stress near the edges of a faceted structure. The observations provide new understanding on the equilibrium structure of nanoscale systems and could have important implications for applications in sensing and actuation.

New Insights into Electronic and Geometric Effects in the Enhanced Photoelectrooxidation of Ethanol Using ZnO Nanorod/Ultrathin Au Nanowire Hybrids

Oxidation of small organic molecules in a fuel cell is a viable method for energy production. However, the key issue is the development of suitable catalysts that exhibit high efficiencies and remain stable during operation. Here, we demonstrate that amine-modified ZnO nanorods on which ultrathin Au nanowires are grown act as an excellent catalyst for the oxidation of ethanol. We show that the modification of the ZnO nanorods with oleylamine not only modifies the electronic structure favorably but also serves to anchor the Au nanowires on the nanorods. The adsorption of OH- species on the Au nanowires that is essential for ethanol oxidation is facilitated at much lower potentials as compared to bare Au nanowires leading to high activity. While ZnO shows negligible electrocatalytic activity under normal conditions, there is significant enhancement in the activity under light irradiation. We demonstrate a synergistic enhancement in the photoelectrocatalytic activity of the ZnO/Au nanowire hybrid and provide mechanistic explanation for this enhancement based on both electronic as well as geometric effects. The principles developed are applicable for tuning the properties of other metal/semiconductor hybrids with potentially interesting applications beyond the fuel cell application demonstrated here.

Room Temperature Growth of Ultrathin Au Nanowires with High Areal Density over Large Areas by in Situ Functionalization of Substrate

Although ultrathin Au nanowires (similar to 2 nm diameter) are expected to demonstrate several interesting properties, their extreme fragility has hampered their use in potential applications. One way to improve the stability is to grow them on substrates; however, there is no general method to grow these wires over large areas. The existing methods suffer from poor coverage and associated formation of larger nanoparticles on the substrate. Herein, we demonstrate a room temperature method for growth of these nanowires with high coverage over large areas by in situ functionalization of the substrate. Using control experiments, we demonstrate that an in situ functionalization of the substrate is the key step in controlling the areal density of the wires on the substrate. We show that this strategy works for a variety of substrates ranging like graphene, borosil glass, Kapton, and oxide supports. We present initial results on catalysis using the wires grown on alumina and silica beads and also extend the method to lithography-free device fabrication. This method is general and may be extended to grow ultrathin Au nanowires on a variety of substrates for other applications.

Synthesis and Characterization of Au@Pt Nanoparticles with Ultrathin Platinum Overlayers

Gold-core platinum-shell (Au@Pt) nanoparticles with ultrathin platinum overlayers, ranging from submonolayer to two monolayers of platinum atoms, were prepared at room-temperature using a scalable, wet-chemical synthesis route. The synthesis involved the reduction of chloroauric acid with tannic acid to form 5 nm (nominal dia.) gold nanoparticles followed by addition of desired amount of chloroplatinic acid and hydrazine to form platinum overlayers with bulk Pt/Au atomic ratios (Pt surface coverages) corresponding to 0.19 (half monolayer), 0.39 (monolayer), 0.58 (1.5 monolayer) and 0.88 (2 monolayers). The colloidal particles were coated with octadecanethiol and phase-transferred into chlroform-hexane mixture to facilitate sample preparation for structural characterization. The structure of the resultant nanoparticles were determined to be Au@Pt using HRTEM, SAED, XPS, UV-vis and confirmed by cyclic voltammetry (CV) studies. Monolayers of octadecanethiol coated Au@Pt nanoparticles were self-assembled at an air-water interface and transfer printed twice onto a gold substrate to form bilayer films for electrochemical characterization. Electrochemical activity on such films was observed only after the removal of the octadecanethiol ligand coating the nanoparticles, using a RF plasma etching process. The electrochemical activity (HOR, MOR studies) of Au@Pt nanoparticles was found to be highest for particles having a two atom thick platinum overlayer. These nanoparticles can significantly enhance platinum utilization in electrocatalytic applications as their platinum content based activity was three times higher than pure platinum nanoparticles.

Ultrathin Au nanowires supported on rGO/TiO2 as an efficient photoelectrocatalyst

We report the synthesis of stable rGO/TiO2/Au nanowire hybrids showing excellent electrocatalytic activity for ethanol oxidation. Phase-pure anatase TiO2 nanoparticles (similar to 3 nm) were grown on GO sheets followed by the growth of ultrathin Au nanowires leading to the formation of a multidimensional ternary structure (0-D TiO2 and 1-D Au on 2-D graphene oxide). The oleylamine used for the synthesis of the Au nanowires not only leads to stable Au nanowires anchored on the GO sheets but also leads to the functionalization and room temperature reduction of GO. Using control experiments, we delineate the role of the three components in the hybrid and show that there is a significant synergy. We show that the catalytic activity for ethanol oxidation primarily stems from the Au nanowires. While TiO2 triggers the formation of oxygenated species on the Au nanowire surface at a lower potential and also imparts photoactivity, rGO provides a conducting support to minimize the charge transfer resistance in addition to stabilizing the Au nanowires. Compared with nanoparticle hybrids, the nanowire hybrids display a much better electrocatalytic performance. In addition to high efficiency, the nanowire hybrids also show a remarkable tolerance towards H2O2. While our study has a direct bearing on fuel cell technology, the insights gained are sufficiently general such that they provide guiding principles for the development of multifunctional ternary hybrids.

Directed Assembly of Ultrathin Gold Nanowires over Large Area by Dielectrophoresis

Ultrathin Au nanowires (similar to 2 nm diameter) are interesting from a fundamental point of view to study structure and electronic transport and also hold promise in the field of nanoelectronics, particularly for sensing applications. Device fabrication by direct growth on various substrates has been useful in demonstrating some of the potential applications. However, the realization of practical devices requires device fabrication strategies that are fast, inexpensive, and efficient. Herein, we demonstrate directed assembly of ultrathin Au nanowires over large areas across electrodes using ac dielectrophoresis with a mechanistic understanding of the process. On the basis of the voltage and frequency, the wires either align in between or across the contact pads. We exploit this assembly to produce an array of contacting wires for statistical estimation of electrical transport with important implications for future nanoelectronic/sensor applications.

Graphene-oxide-supported ultrathin Au nanowires: efficient electrocatalysts for borohydride oxidation

We report stable ultrathin Au nanowires supported on reduced graphene oxide with outstanding electrocatalytic activity for borohydride oxidation. Electrochemical impedance spectroscopy measurements showed abnormal inductive behavior, indicative of surface reactivation. DFT calculations indicate that the origin of the high activity stems from the position of the Au d-band center.

Nanocrystalline Janus films of inorganic materials prepared at the liquid-liquid interface

The interface between toluene and water has been employed to prepare ultrathin Janus nanocrystalline films of metal oxides, metal chalcogenides and gold, wherein the surface on the organic-side is hydrophobic and the aqueous-side is hydrophilic. We have changed the nature of the metal precursor or capping agent in the organic layer to increase the hydrophobicity. The strategy employed for this purpose is to increase the length of the alkane chain in the precursor or use a perfluroalkane derivative as precursor or as a capping agent. The hydrophobicity and hydrophilicity of the Janus films have been determined by contact angle measurements. The morphology of hydrophobic and hydrophilic sides of the film have been examined by field emission scanning electron microscopy.

Buckling in polymer monolayers: Molecular-weight dependence

We present systematic investigations of buckling in Langmuir monolayers of polyvinyl acetate formed at the air-water interface. On compression the polymer monolayers are converted to a continuous membrane with a thickness of ~2–3 nm of well-defined periodicity, lambdab. Above a certain surface concentration the membrane undergoes a morphological transition buckling, leading to the formation of striped patterns. The periodicity seems to depend on molecular weight as per the predictions of the gravity-bending buckling formalism of Milner et al. for fluidlike films on water. However anomalously low values of bending rigidity and Young's modulus are obtained using this formalism. Hence we have considered an alternative model of buckling-based solidlike films on viscoelastic substrates. The values of bending rigidity and Young's modulus obtained by this method, although lower than expected, are closer to the bulk values. Remarkably, no buckling is found to occur above a certain molecular weight. We have tried to explain the observed molecular-weight dependence in terms of the variation in isothermal compressive modulus of the monolayers with surface concentration as well as provided possible explanations for the obtained low values of mechanical properties similar to that observed for ultrathin polymer films.

Morphological transitions in polymer monolayers under compression

We present a systematic investigation of morphological transitions in poly vinylacetate Langmuir monolayers. On compression, the polymer monolayer is converted to a continuous membrane with a thickness of similar to 2-3 nm. Above a certain surface concentration the monolayer, on water, undergoes a morphological transition-buckling, leading to formation of striped patterns of period of lambda(b)similar to 160 nm, as determined from in situ grazing incidence small angle x-ray scattering measurements. The obtained value is much smaller than what has been typically observed for Langmuir monolayers on water or thin films on soft substrates. Using existing theories for buckling of fluidlike films on fluid substrates, we obtain very low values of bending rigidity and Young's modulus of the polymer monolayer compared to that observed earlier for lipid or polymeric monolayers. Since buckling in these monolayers occurs only above a certain surface concentration, we have looked at the possibility that the buckling in these films occurs due to changes in their mechanical properties under compression. Using the model of Huang and Suo of buckling of solidlike films on viscoelastic substrates, we find values of the mechanical properties, which are much closer to the bulk values but still significantly lower. Although the reduction could be along the lines of what has been observed earlier for ultrathin polymer film or surface layers of polymers, the possibility of micromechanical effects also determining the buckling in such polymer monolayers cannot be ruled out. We have provided possible explanation of the buckling of the poly vinylacetate monolayers in terms of the change in isothermal compression modulus with surface concentration.

The formation of carbon nanostructures by in situ TEM mechanical nanoscale fatigue and fracture of carbon thin films

A technique to quantify in real time the microstructural changes occurring during mechanical nanoscale fatigue of ultrathin surface coatings has been developed. Cyclic nanoscale loading, with amplitudes less than 100 nm, is achieved with a mechanical probe miniaturized to fit inside a transmission electron microscope (TEM). The TEM tribological probe can be used for nanofriction and nanofatigue testing, with 3D control of the loading direction and simultaneous TEM imaging of the nano-objects. It is demonstrated that fracture of 10-20 nm thick amorphous carbon films on sharp gold asperities, by a single nanoscale shear impact, results in the formation of < 10 nm diameter amorphous carbon filaments. Failure of the same carbon films after cyclic nanofatigue, however, results in the formation of carbon nanostructures with a significant degree of graphitic ordering, including a carbon onion.

Surface-enhanced Raman scattering of molecules adsorbed on nanocrystalline Au and Ag films formed at the organic-aqueous interface

Surface-enhanced Raman scattering (SERS) of pyridine adsorbed on ultrathin nanocrystalline Au and Ag films generated at the liquid-liquid interface has been investigated. The shifts and intensification of bands formed with these films comprising metal nanoparticles are comparable to those found with other types of Au and Ag substrates. SERS of rhodamine 6G adsorbed on Ag films has also been studied. The results demonstrate that nanocrystalline metal films prepared by the simple method involving the organic-aqueous interface can be used effectively for SERS investigations.

Electroconductance in single-wall carbon nanotubes

A comparative study of the electric-field induced hopping transport probes the effective dimensionality (D) in bulk and ultrathin films of single-wall carbon nanotubes (SWNTs). The values of the scaling function exponents for the electroconductance are found to be consistent with that in three-dimensional and two-dimensional systems. The significant difference in threshold voltage in these two types of SWNTs is a consequence of the variation in the number of energetically favorable sites available for charge carriers to hop by using the energy from the field. Furthermore, a modification to the magnetotransport is observed under high electric-fields.

Viscoelastic Properties of Nanocrystalline Films of Semiconducting Chalcogenides at Liquid/Liquid Interface

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3−5 nm in diameter) formed at toluene−water interfaces have been studied. The ultrathin films (50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene−water interface between a metal−organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D “soft” materials like gels, foams, and concentrated colloidal suspensions can be described by the “soft” glassy rheology model.