Methanol, ethanol and hydrogen sensing using metal oxide and metal (TiO(2)-Pt) composite nanoclusters on GaN nanowires: a new route towards tailoring the selectivity of nanowire/nanocluster chemical sensors

We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO(2)) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO(2)-Pt) nanowire-nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO(2) sensors. The GaN/TiO(2) NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO(2) sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO(2)-Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol(-1) (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 μmol mol(-1) (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential for tailoring the selectivity of the hybrid nanosensors for a multitude of environmental and industrial sensing applications.     

Hybrid AlGaN/GaN-ZnO-nanowire gas sensors

The potential of AIGaN/GaN heterostructures integrated with zinc oxide (ZnO) nanowires for gas sensing applications is demonstrated. Single crystal ZnO nanowires, serving as sensing probes, were selectively grown between two ohmic electrodes of AIGaN/GaN two dimensional electron gas heterostructures by thermal oxidation of sputtered zinc films in air. Electron diffraction and transmission electron microscopy showed the ZnO-nanowires to be crystalline structures oriented in the [001] direction. The fabricated structures were used to detect ethanol, acetone and methanol in a nitrogen background. The results indicate that the hybrid AIGaN/GaN-ZnO nanowires gas sensors are operable over a broad range of temperatures and could potentially be integrated with devices for wireless environmental monitoring.     

Acoustic charge transport in GaN nanowires

We present acoustic charge transport in GaN nanowires (GaN NWs). The GaN NWs were grown by molecular beam epitaxy (MBE) on silicon(111) substrates. The nanowires were removed from the silicon substrate, aligned using surface acoustic waves (SAWs) on the piezoelectric substrate LiNbO(3) and finally contacted by electron beam lithography. Then, a SAW was used to create an acoustoelectric current in the GaN NWs which was detected as a function of radio-frequency (RF) wave frequency and its power. The presented method and our experimental findings open up a route towards new acoustic charge transport nanostructure devices in a wide bandgap material such as GaN.     

Controlled dielectrophoretic nanowire self-assembly using atomic layer deposition and suspended microfabricated electrodes

Effects of design and materials on the dielectrophoretic self-assembly of individual gallium nitride nanowires (GaN NWs) onto microfabricated electrodes have been experimentally investigated. The use of TiO(2) surface coating generated by atomic layer deposition (ALD) improves dielectrophoretic assembly yield of individual GaN nanowires on microfabricated structures by as much as 67%. With a titanium dioxide coating, individual nanowires were placed across suspended electrode pairs in 46% of tests (147 out of 320 total), versus 28% of tests (88 out of 320 total tests) that used uncoated GaN NWs. An additional result from these tests was that suspending the electrodes 2.75 μm above the substrate corresponded with up to 15.8% improvement in overall assembly yield over that of electrodes fabricated directly on the substrate.     

Self-assembled GaN nanowires on diamond

We demonstrate the nucleation of self-assembled, epitaxial GaN nanowires (NWs) on (111) single-crystalline diamond without using a catalyst or buffer layer. The NWs show an excellent crystalline quality of the wurtzite crystal structure with m-plane faceting, a low defect density, and axial growth along the c-axis with N-face polarity, as shown by aberration corrected annular bright-field scanning transmission electron microscopy. X-ray diffraction confirms single domain growth with an in-plane epitaxial relationship of (10 ?10)(GaN) [parallel] (01 ?1)(Diamond) as well as some biaxial tensile strain induced by thermal expansion mismatch. In photoluminescence, a strong and sharp excitonic emission reveals excellent optical properties superior to state-of-the-art GaN NWs on silicon substrates. In combination with the high-quality diamond/NW interface, confirmed by high-resolution transmission electron microscopy measurements, these results underline the potential of p-type diamond/n-type nitride heterojunctions for efficient UV optoelectronic devices.     

Structural and optical properties of glancing angle deposited TiO2 nanowires array

TiO2 nanowires (NWs) have been synthesized by glancing angle deposition technique using e-beam evaporator. The average length 490 nm and diameter 80 nm of NWs were examined by field emission-scanning electron microscopy. Transmission electron microscopy emphasized that the NWs were widely dispersed at the top. X-ray diffraction has been carried out on the TiO2 thin film (TF) and NW array. A small blue shift of 0.03 eV was observed in Photoluminescence (PL) main band emission for TiO2 NW as compared to TiO2 TF. The high temperature annealing at 980 degrees C partially removed the oxygen vacancy from the sample, which was investigated by PL and optical absorption measurements.     

Fabrication of GaN/GaN:Mn core/shell nanowires and their photoluminescences

We report on the fabrication of GaN/GaN:Mn core/shell nanowires (NWs) using a two-step metalorganic chemcial vapor deposition (MOCVD) and chloride-based chemical vapor transport (CVT) process. Structural analyses indicated that the heterostructure NWs were single crystalline and exhibited a core/shell and lozenge structure. The photoluminescence (PL) of the core/shell NWs showed a peak at a center wavelength of 454 nm, which was red-shifted compared to those of GaN and GaN:Mn NWs. This outcome indicates the accumulation of excited carriers at the interfaces that would be helpful in developing novel magnetism in diluted magnetic GaN:Mn semiconductors.     

Hybrid Films of Graphene and Carbon Nanotubes for High Performance Chemical and Temperature Sensing Applications

A hybrid composite material of graphene and carbon nanotube (CNT) for high performance chemical and temperature sensors is reported. Integration of 1D and 2D carbon materials into hybrid carbon composites is achieved by coupling graphene and CNT through poly(ionic liquid) (PIL) mediated‐hybridization. The resulting CNT/PIL/graphene hybrid materials are explored as active materials in chemical and temperature sensors. For chemical sensing application, the hybrid composite is integrated into a chemo‐resistive sensor to detect a general class of volatile organic compounds. Compared with the graphene‐only devices, the hybrid film device showed an improved performance with high sensitivity at ppm level, low detection limit, and fast signal response/recovery. To further demonstrate the potential of the hybrid films, a temperature sensor is fabricated. The CNT/PIL/graphene hybrid materials are highly responsive to small temperature gradient with fast response, high sensitivity, and stability, which may offer a new platform for the thermoelectric temperature sensors.     

Study of using aqueous NH3 to synthesize GaN nanowires on Si(1 1 1) by thermal chemical vapor deposition

High-quality GaN nanowires (NWs) and zigzag-shaped NWs were grown on catalyst-free Si(1 1 1) substrate by thermal chemical vapor deposition (TCVD). Gallium (Ga) metal and aqueous NH₃ solution are used as a source of materials. Ga vapor was directly reacts with gaseous NH₃ under controlled nitrogen flow at 1050 °C. Scanning electron microscopy (SEM) images showed that the morphology of GaN displayed various densities of NWs and zigzag NWs depending on the gas flow rate, and increased nitrogen flow rate caused density reduction. The GaN NWs exhibited clear X-ray diffraction analysis (XRD) peaks that corresponded to GaN with hexagonal wurtzite structures. The photoluminescence spectra showed that the ultraviolet band emission of GaN NWs had a strong near band-edge emission (NBE) at 361–367 nm. Yellow band emissions were observed at low and high flow rates due to nitrogen and Ga vacancies, respectively. Moderate N₂ flow resulted in a strong NBE emission and a high optical quality of the NWs. This study shows the possibility of low-cost synthesis of GaN nanostructures on Si wafers using aqueous NH₃ solution.     

Water vapor detection with individual tin oxide nanowires

Individual tin oxide nanowires (NWs), contacted to platinum electrodes using focused ion beam assisted nanolithography, were used for detecting water vapor (1500-32?000?ppm) in different gaseous environments. Responses obtained in synthetic air (SA) and nitrogen atmospheres suggested differences in the sensing mechanism, which were related to changes in surface density of the adsorbed oxygen species in the two cases. A model describing the different behaviors has been proposed together with comparative evaluation of NW responses against sensors based on bulk tin oxide. The results obtained on ten?individual devices (tested >6 times) revealed the interfering effect of water in the detection of carbon monoxide and illustrated the intrinsic potential of nanowire-based devices as humidity sensors. Investigations were made on sensitivity, recovery time and device stability as well as surface-humidity interactions. This is the first step towards fundamental understanding of single-crystalline one-dimensional (1D) tin oxide nanostructures for sensor applications, which could lead to integration in real devices.     

Selective area growth of GaN nanowires using metalorganic chemical vapor deposition on nano-patterned Si(111) formed by the etching of nano-sized Au droplets

We report on the selective area growth of GaN nanowires (NWs) on nano-patterned Si(111) substrates by metalorganic chemical vapor deposition. The nano-patterns were fabricated by the oxidation of Si followed by the etching process of Au nano-droplets. The size of formed nano-pattern on Si(111) substrate was corresponding to the size of Au nano-droplet, and the diameter of GaN NWs grown was similar to the diameter of fabricated nano-pattern. The interesting phenomenon of using the nano-patterned Si(111) substrates is the formation of very clear substrate surface even after the growth of GaN NWs. However, in the case of GaN NWs grown using Au nano-droplets, there was several nanoparticles including GaN bulk grains on the Si(111) substrates. The smooth surface morphology of nano-patterned Si(111) substrates was attributed to the presence of SiO₂ layer which prevents the formation of unnecessary GaN particles during the GaN NW growth. Therefore, we believe that nano-patterning method of Si(111) which was obtained by the oxidation of Si(111) substrate and subsequent Au etching process can be utilized to grow high-quality GaN NWs and its related nano-device applications.     

Nucleation and growth of GaN nanowires on Si(111) performed by molecular beam epitaxy

GaN nanowires (NWs) have been grown on Si(111) substrates by plasma-assisted molecular beam epitaxy (PAMBE). The nucleation process of GaN-NWs has been investigated in terms of nucleation density and wire evolution with time for a given set of growth parameters. The wire density increases rapidly with time and then saturates. The growth period until the nucleation of new nanowires is terminated can be defined as the nucleation stage. Coalescence of closely spaced nanowires reduces the density for long deposition times. The average size of the well-nucleated NWs shows linear time dependence in the nucleation stage. High-resolution transmission electron microscopy measurements of alternating GaN and AlN layers give valuable information about the length and radial growth rates for GaN and AlN in NWs.     

Synthesis of vertically oriented GaN nanowires on a LiAlO2 substrate via chemical vapor deposition

Vertically oriented nanowires (NWs) of single-crystalline wurtzite GaN have been fabricated on γ-LiAlO₂ (100) substrate coated with a Au layer, via a chemical vapor deposition process at 1000 °C using gallium and ammonia as source materials. The GaN NWs grow along the nonpolar [100] direction with steeply tapering tips, and have triangular cross-sections with widths of 50–100 nm and lengths of up to several microns. The GaN NWs are formed by a vapor-liquid-solid growth mechanism and the tapering tips are attributed to the temperature decrease in the final stage of the synthesis process. The aligned GaN NWs show blue-yellow emission originating from defect levels, residual impurities or surface states of the GaN NWs, and have potential applications in nanotechnology.     

Sol-gel-coated mid-infrared fiber-optic sensors

Application of organically modified sol-gels as novel recognition membranes for mid-infrared fiber-optic sensors is demonstrated for the first time by in situ detection of nitro-based aromatic compounds in aqueous media. Sol-gels were prepared by acid- and base-catalyzed copolymerization of alkyltrimethoxysiloxanes and applied onto the surface of silver halide (AgCl(0.3)Br(0.7)) fibers by drip coating. The coating process was monitored in situ using Fourier transform infrared (FT-IR) spectroscopy. Homogeneity of the layers was analyzed by scanning electron microscopy. Sol-gel-coated evanescent held sensors were investigated with respect to their capacity to suppress interfering water background absorptions, repeatability of dissolved analyte enrichment, and sensor response time. Nitrobenzene and parathion are the investigated analytes; figures of merit are derived from calibration curves determined to assess sensitivity and reproducibility of the developed sensor system. It can be concluded that sol-gel-coated infrared fiber-optic sensors enable reproducible detection of nitro-based aromatic compounds in the low ppm concentration range. Due to wide flexibility in tuning chemical properties of sol-gel films along with superior mechanical and chemical stability, organically modified sol-gels represent highly interesting coating materials for mid-infrared sensing applications.     

Platinum-nanoparticle-modified TiO2 nanowires with enhanced photocatalytic property

Highly crystalline Pt nanoparticles with an average diameter of 5 nm were homogeneously modified on the surfaces of TiO(2) nanowires (Pt-TiO(2) NWs) by a simple hydrothermal and chemical reduction route. Photodegradation of methylene blue (MB) in the presence of Pt-TiO(2) NWs indicates that the photocatalytic activity of TiO(2) NWs can be greatly enhanced by Pt nanoparticle modification. The physical chemistry process and photocatalytic mechanism for Pt-TiO(2) NWs hybrids degrading MB were investigated and analyzed. The Pt attached on TiO(2) nanowires induces formation of a Schottky barrier between TiO(2) and Pt naonoparticles, leading to a fast transport of photogenerated electrons to Pt particles. Furthermore, Pt incoporation on TiO(2) surface can accelerate the transfer of electrons to dissolved oxygen molecules. Besides enhancing the electron-hole separation and charge transfer to dissolved oxygen, Pt may also serve as an effective catalyst in the oxidation of MB. However, a high Pt loading value does not mean a high photocatalytic activity. Higher content loaded Pt nanoparticles can absorb more incident photons which do not contribute to the photocatalytic efficiency. The highest photocatalytic activity for the Pt-TiO(2) nanohybrids on MB can be obtained at 1 at % Pt loading.     

Impact of Device Technology Processes on the Surface Properties and Biocompatibility of Group III Nitride Based Sensors

In this work we have investigated the impact of typical device processing steps on the surface properties (roughness, chemical composition, contact angle to water) of group III‐nitride based chemical sensors with emphasis on the electrical performance of the sensor and the biocompatibility. Basic sensing device is an AlGaN/GaN high electron mobility transistor. The widely distributed mammalian cell cultures HEK 293FT and CHO‐K1 served as biological model systems. The processing of the devices had only little influence on the cell growth onto the sensor. In all cases it was superior to silicon surfaces. Fluorine dry etching smoothes the surface and forms an oxide, which improves the electrical properties of the AlGaN/GaN sensor. In contrast, autoclave treatment enhances the carbon contamination with negative impact on the sensor properties and increased the contact angle to water. For all other treatments the contact angle recaptures a value of about 50 ± 5° after exposure to air or water droplets for some hours due to the contamination by hydrocarbons.     

Field effect transistor from individual trigonal Se nanowire

Trigonal Se nanowires (NWs) were fabricated through a high-yield chemical solution process. The morphology and structural characterization of the Se NWs were investigated using transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and x-ray diffraction (XRD). The results indicated that the Se NWs grow along the crystallographic c-axis, the direction of which is parallel to the helical chains of Se atoms. Single Se NW field effect transistor (FET) devices were prepared through photolithographic patterning. The device performance shows that the Se NWs are p-type semiconductors displaying mobility up to 30?cm(2)?V(-1)?s(-1). This finding on the Se NW FETs has broad implications and provides very useful fundamental information necessary for future applications in the fabrication of high-quality NW FETs and other electronic devices.     

High output nanogenerator based on assembly of GaN nanowires

GaN nanowires (NWs) were synthesized through a vapor-liquid-solid (VLS) process. Based on structural analysis, the c-axis of the NW was confirmed to be perpendicular to the growth direction. Nanogenerators (NGs) fabricated by rational assembly of the GaN NWs produced an output voltage up to 1.2 V and output current density of 0.16 μA cm?2. The measured performance of the GaN NGs was consistent with the calculations using finite element analysis (FEA).     

General control of transition-metal-doped GaN nanowire growth: toward understanding the mechanism of dopant incorporation

We report the first synthesis and characterization of cobalt- and chromium-doped GaN nanowires (NWs), and compare them to manganese-doped GaN NWs. Samples were synthesized by chemical vapor deposition method, using cobalt(II) chloride and chromium(III) chloride as dopant precursors. For all three impurity dopants hexagonal, triangular, and rectangular NWs were observed. The fraction of NWs having a particular morphology depends on the initial concentration of the dopant precursors. While all three dopant ions have the identical effect on GaN NW growth and faceting, Co and Cr are incorporated at much lower concentrations than Mn. These findings suggest that the doping mechanism involves binding of the transition-metal intermediates to specific NW facets, inhibiting their growth and causing a change in the NW morphology. We discuss the doping concentrations of Mn, Co, and Cr in terms of differences in their crystal-field stabilization energies (DeltaCFSE) in their gas-phase intermediates and in substitutionally doped GaN NWs. Using iron(III) chloride and cobalt(II) acetate as dopant precursors we show that the doping concentration dependence on DeltaCFSE allows for the prediction of achievable doping concentrations for different dopant ions in GaN NWs, and for a rational choice of a suitable dopant-ion precursor. This work further demonstrates a general and rational control of GaN NW growth using transition-metal impurities.     

Pd nanowires as new biosensing materials for magnified fluorescent detection of nucleic acid

The designed synthesis of new nanomaterials with controlled shape, composition, and structure is critical for tuning their physical and chemical properties, and further developing interesting analytical sensing devices. Herein, we presented that Pd nanowires (NWs) can be used as a new biosensing platform for high-sensitivity nucleic acid detection. The general sensing concept is based on the fact that Pd NWs can adsorb the fluorescently labeled single-stranded DNA probe and lead to substantial fluorescence quenching of dye, followed by specific hybridization with the complementary region of the target DNA sequence. This results in desorption of double-stranded DNA from Pd NWs surface and subsequent recovery of fluorescence. Furthermore, an amplification strategy based on Pd NWs for nucleic acid detection by using exonuclease III (Exo III) was demonstrated. The present dual-magnification sensing system combined Pd NWs with Exo III has a detection range of 1.0 nM to 2.0 μM with the detection limit of 0.3 nM (S/N = 3), which is about 20-fold higher than that of traditional unamplified homogeneous assays.