Sensitivity-tuned CO gas sensors with tailored Ga-doping in ZnO nanowires

Sensitivity-customization of zinc oxide (ZnO) nanowire (NW) gas sensors has been demonstrated by controlling Ga-doping, thereby tuning the resistance of the NWs. Both un-doped and 5 weight% Ga-doped ZnO (GZO) NWs are synthesized for the highly sensitive sensing within a narrow detection window and a less sensitive one within an expanded window, respectively. We have employed hot-walled pulsed laser deposition (HW-PLD) for the NW synthesis. With CO gas injection, the resistance reduction of NWs is detected and analyzed in a self-designed gas chamber that guarantees the precise control of gas flow and, gas concentration, as well as temperature. NW sensitivity is proportional to the sensing temperature and inversely proportional to the doping concentration resulting in widening the sensing window up to 230 times by the 5 wt.% Ga-doping.     

ZnO nanowire co-growth on SiO2 and C by carbothermal reduction and vapour advection

Vertically aligned ZnO nanowires (NWs) were grown on Au-nanocluster-seeded amorphous SiO(2) films by the advective transport and deposition of Zn vapours obtained from the carbothermal reaction of graphite and ZnO powders. Both the NW volume and visible-to-UV photoluminescence ratio were found to be strong functions of, and hence could be tailored by, the (ZnO+C) source-SiO(2) substrate distance. We observe C flakes on the ZnO NWs/SiO(2) substrates which exhibit short NWs that developed on both sides. The SiO(2) and C substrates/NW interfaces were studied in detail to determine growth mechanisms. NWs on Au-seeded SiO(2) were promoted by a rough ZnO seed layer whose formation was catalysed by the Au clusters. In contrast, NWs grew without any seed on C. A correlation comprising three orders of magnitude between the visible-to-UV photoluminescence intensity ratio and the NW volume is found, which results from a characteristic Zn partial pressure profile that fixes both O deficiency defect concentration and growth rate.     

Rational synthesis of p-type zinc oxide nanowire arrays using simple chemical vapor deposition

We report, for the first time, the synthesis of the high-quality p-type ZnO NWs using a simple chemical vapor deposition method, where phosphorus pentoxide has been used as the dopant source. Single-crystal phosphorus doped ZnO NWs have their growth axis along the 001 direction and form perfect vertical arrays on a-sapphire. P-type doping was confirmed by photoluminescence measurements at various temperatures and by studying the electrical transport in single NWs field-effect transistors. Comparisons of the low-temperature PL of unintentionally doped ZnO (n-type), as-grown phosphorus-doped ZnO, and annealed phosphorus-doped ZnO NWs show clear differences related to the presence of intragap donor and acceptor states. The electrical transport measurements of phosphorus-doped NW FETs indicate a transition from n-type to p-type conduction upon annealing at high temperature, in good agreement with the PL results. The synthesis of p-type ZnO NWs enables novel complementary ZnO NW devices and opens up enormous opportunities for nanoscale electronics, optoelectronics, and medicines.     

An advanced fabrication method of highly ordered ZnO nanowire arrays on silicon substrates by atomic layer deposition

In this work, the controlled fabrication of highly ordered ZnO nanowire (NW) arrays on silicon substrates is reported. Si NWs fabricated by a combination of phase shift lithography and etching are used as a template and are subsequently substituted by ZnO NWs with a dry-etching technique and atomic layer deposition. This fabrication technique allows the vertical ZnO NWs to be fabricated on 4 in Si wafers. Room temperature photoluminescence and micro-photoluminescence are used to observe the optical properties of the atomic layer deposition (ALD) based ZnO NWs. The sharp UV luminescence observed from the ALD ZnO NWs is unexpected for the polycrystalline nanostructure. Surprisingly, the defect related luminescence is much decreased compared to an ALD ZnO film deposited at the same time ona plane substrate. Electrical characterization was carried out by using nanomanipulators. With the p-type Si substrate and the n-type ZnO NWs the nanodevices represent p–n NW diodes.The nanowire diodes show a very high breakthrough potential which implies that the ALD ZnO NWs can be used for future electronic applications.     

Partial conversion reaction of ZnO nanowires to ZnSe by a simple selenization method and their photocatalytic activities

A simple novel synthetic method for preparing ZnSe/ZnO heterostructured nanowire (NW) arrays via the selenization of ZnO NWs is reported. A hydrothermally grown ZnO NWs array on a glass substrate was reacted with selenium vapor to generate a 20–30 nm of zincblend ZnSe nanoparticles (NPs) on wurtzite ZnO NWs. A growth mechanism was proposed based on SEM, XRD, and TEM analysis to explain the partial chemical conversion of ZnO NW surfaces into ZnSe NPs. This mechanism is applicable to the synthesis of other chalcogenide compounds. The as-synthesized ZnSe/ZnO heterojunctions showed enhanced UV–visible light absorption properties. The materials exhibited excellent photocatalytic activity toward the decomposition of an organic dye compared to the bare ZnO due to enhanced light absorption and the type-II cascade band structure.     

Highly efficient visible light photocatalysis of novel CuS/ZnO heterostructure nanowire arrays

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu(2)S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.     

A ZnO nanowire vacuum pressure sensor

In this study, we report the growth and characterization of lateral ZnO nanowires (NWs) on ZnO:Ga/glass templates. Using x-ray diffraction and micro-Raman spectroscopy, it was found that crystal quality of the as-grown ZnO NWs is good. It was also found that the average length and average diameter of the laterally grown ZnO NWs were 5?μm and 30?nm, respectively. A vacuum pressure sensor was then fabricated using a single NW bridging across two electrodes. By measuring the current-voltage characteristics of the samples at low pressure, we found that the currents were of 17, 34.28, 57.37 and 96.06?nA for the ZnO NW measured at 1 × 10(-3)?Torr, 1 × 10(-4)?Torr, 3 × 10(-5)?Torr and 5 × 10(-6)?Torr, respectively. These values suggest that the laterally grown ZnO NWs prepared in this study are potentially useful for vacuum pressure sensing.     

The growth of porous ZnO nanowires by thermal oxidation of ZnS nanowires

The growth of porous ZnO nanowires (NWs) via phase transformation of ZnS NWs at 500-850 degrees C in air was studied. The ZnS NWs were first synthesized by thermal evaporation of ZnS powder at 1100 degrees C in Ar. On subsequent annealing at 500 degrees C in air, discrete ZnO epilayers formed on the surface of ZnS NWs. At 600 degrees C, polycrystalline ZnO and the crack along the (0001) interface between the ZnO epilayer and ZnS NW were observed. At 700-750 degrees C ZnS NWs transformed to ZnO NWs, meanwhile nanopores and interfacial cracks were observed in the ZnO NWs. Two factors, the evaporation of SO2 and SO3 and the stress induced by the incompatible structure at the interface of ZnO epilayer and ZnS NW, can be responsible for the formation of porous ZnO NWs from ZnS NW templates on annealing at 700-750 degrees C in air. Rapid growth of ZnO at 850 degrees C could heal the pores and cracks and thus resulted in the well-crystallized ZnO NWs.     

An aqueous solution-based doping strategy for large-scale synthesis of Sb-doped ZnO nanowires

An aqueous solution-based doping strategy was developed for controlled doping impurity atoms into a ZnO nanowire (NW) lattice. Through this approach, antimony-doped ZnO NWs were successfully synthesized in an aqueous solution containing zinc nitrate and hexamethylenetetramine with antimony acetate as the dopant source. By introducing glycolate ions into the solution, a soluble antimony precursor (antimony glycolate) was formed and a good NW morphology with a controlled antimony doping concentration was successfully achieved. A doping concentration study suggested an antimony glycolate absorption doping mechanism. By fabricating and characterizing NW-based field effect transistors (FETs), stable p-type conductivity was observed. A field effect mobility of 1.2 cm(2) V(-1) s(-1) and a carrier concentration of 6 × 10(17) cm(-3) were achieved. Electrostatic force microscopy (EFM) characterization on doped and undoped ZnO NWs further illustrated the shift of the metal-semiconductor barrier due to Sb doping. This work provided an effective large-scale synthesis strategy for doping ZnO NWs in aqueous solution.     

Heterojunction solar cells with integrated Si and ZnO nanowires and a chalcopyrite thin film

ZnO nanowires (NWs) have been successfully synthesized using a hydrothermal technique on both glass and silicon substrates initially coated with a sputtered ZnO thin film layer. Varying ZnO seed layer thicknesses were deposited to determine the effect of seed layer thickness on the quality of ZnO NW growth. The effect of growth time on the formation of ZnO NWs was also studied. Experimental results show that these two parameters have an important effect on formation, homogeneity and vertical orientation of ZnO NWs. Silicon nanowires were synthesized by a Ag-assisted electroless etching technique on an n-type Si (100) wafer. SEM observations have revealed the formation of vertically-aligned Si NWs with etching depth of ∼700 nm distributed over the surface of the Si. An electron-beam evaporated chalcopyrite thin film consisting of p-type AgGa_0.5In_0.5Se₂ with ∼800 nm thickness was deposited on the n-type ZnO and Si NWs for the construction of nanowire based heterojunction solar cells. For the Si NW based solar cell, from a partially illuminated area of the solar cell, the open-circuit voltage, short-circuit current density, fill factor and power conversion efficiency were 0.34 V, 25.38 mA cm⁻², 63% and 5.50%, respectively. On the other hand, these respective parameters were 0.26 V, 3.18 mA cm⁻², 35% and 0.37% for the ZnO NW solar cell.     

Localized joule heating as a mask-free technique for the local synthesis of ZnO nanowires on silicon nanodevices

We report a mask-free technique for the local synthesis of ZnO nanowires (NWs) on polysilicon nanobelts and polysilicon NW devices. First, we used localized joule heating to generate a poly(methyl methacrylate) (PMMA) nanotemplate, allowing the rapid and self-aligned ablation of PMMA within a short period of time (ca. 5 μs). Next, we used ion-beam sputtering to prepare an ultrathin Au film and a ZnO seed layer; a subsequent lift-off process left the seed layers selectively within the PMMA nanotemplate. Gold nanoparticles and ZnO NWs were formed selectively in the localized joule heating region.     

Preferential growth of ZnO thin films by the atomic layer deposition technique

Preferred orientation of ZnO thin films deposited by the atomic layer deposition (ALD) technique could be manipulated by deposition temperature. In this work, diethyl zinc (DEZn) and deionized water (H(2)O) were used as a zinc source and oxygen source, respectively. The results demonstrated that (10.0) dominant ZnO thin films were grown in the temperature range of 155-220?°C. The c-axis crystal growth of these films was greatly suppressed. Adhesion of anions (such as fragments of an ethyl group) on the (00.2) polar surface of the ZnO thin film was believed to be responsible for this suppression. In contrast, (00.2) dominant ZnO thin films were obtained between 220 and 300?°C. The preferred orientations of (10.0) and (00.2) of the ZnO thin films were examined by XRD texture analysis. The texture analysis results agreed well with the alignments of ZnO nanowires (NWs) which were grown from these ZnO thin films. In this case, the nanosized crystals of ZnO thin films acted as seeds for the growth of ZnO nanowires (NWs) by chemical vapor deposition (CVD) process. The highly (00.2) textured ZnO thin films deposited at high temperatures, such as 280?°C, contained polycrystals with the c?axis perpendicular to the substrate surface and provided a good template for the growth of vertically aligned ZnO NWs.     

Diameter-dependent thermal transport in individual ZnO nanowires and its correlation with surface coating and defects

A systematic study of the thermal transport properties of individual single-crystal zinc oxide (ZnO) nanowires (NWs) with diameters in the range of ～50-210 nm is presented. The thermal conductivity of the NWs is found to be dramatically reduced by at least an order of magnitude compared to bulk values, due to enhanced phonon-boundary scattering with a reduction in sample size. While the conventional phonon transport model can qualitatively explain the temperature dependence, it fails to account for the diameter dependence. An empirical relationship for assessing diameter-dependent thermal properties is observed, which shows an approximately linear dependence of the thermal conductivity on the cross-sectional area of the NWs in the measured diameter range. Furthermore, it is found that an amorphous-carbon layer coating on the NWs does not perturb the thermal properties of the NW cores, whereas 30 keV Ga(+) ion irradiation at low dose (～4 × 10(14) cm(-2)) leads to a remarkable reduction of the thermal conductivity of the ZnO NWs.     

The effect of metal layers on the morphology and optical properties of hydrothermally grown zinc oxide nanowires

If the silicon industry is to successfully integrate ZnO nanowires (NWs) into existing devices to fully utilise the piezoelectric or optical properties of ZnO NWs, then a detailed understanding of the effect of metal interconnects on the morphology of the NWs during growth needs to be obtained. In this study, ZnO NWs were hydrothermally grown at 90 °C on Au, Ni and a Si substrate control to mimic the typical surfaces of a MetalMUMPs MEMS chip. The growth rate was significantly affected by the metal film below the ZnO seed layer, which was mainly attributed to changes in the roughness and grain size of the seed layer deposited, with the growth rate decreasing with increasing roughness. The growth rate on Si and Au surfaces also increased when isolated from the Ni samples, suggesting that Ni cations released in the solution could also inhibit growth by electrostatically attaching to the NWs surface and acting as a barrier to the incorporation of zinc ions. Furthermore, photoluminescence studies show the addition of metal layers to the substrate reduces the optical quality of the produced ZnO NWs.     

Optimization of CVD parameters for long ZnO NWs grown on ITO/glass substrate

The optimization of chemical vapour deposition (CVD) parameters for long and vertically aligned (VA) ZnO nanowires (NWs) were investigated. Typical ZnO NWs as a single crystal grown on indium tin oxide (ITO)-coated glass substrate were successfully synthesized. First, the conducted side of ITO–glass substrate was coated with zinc acetate dihydrate to form seed layer of ZnO nanocrystals. Double zone tube furnace connected to vacuum pump was used for ZnO growth process. Zn metal powder was positioned at the first zone at temperature 900 ^° C. The ITO–glass substrate with pre-coated seed layer was then located in the second zone of tube furnace at growth temperature of 550 ^° C. The growth of ZnO NWs was controlled under constant concentration of seed layer, while other parameters such as argon and oxygen flow rates, substrate position, time and oxygen flow rate were varied. The VA ZnO NWs were finally characterized by scanning electron microscopy, X-ray diffractometer and high-resolution transmission electron microscope equipped with energy-dispersive X-ray spectroscopy. The results show that long and VA ZnO NWs were single crystalline with hexagonal wurtzite structure. The ultimate length and average diameter of ZnO NWs were 10 μm and 50–100 nm, respectively. These were achieved under optimized CVD growth parameters. The mechanism of vertical growth model of ZnO NWs is also discussed.     

Near-ultraviolet zinc oxide nanowire sensor using low temperature hydrothermal growth

Two near-ultraviolet (UV) sensors based on solution-grown zinc oxide (ZnO) nanowires (NWs) which are only sensitive to photo-excitation at or below 400?nm wavelength have been fabricated and characterized. Both devices keep all processing steps, including nanowire growth, under 100?°C for compatibility with a wide variety of substrates. The first device type uses a single optical lithography step process to allow simultaneous in?situ horizontal NW growth from solution and creation of symmetric ohmic contacts to the nanowires. The second device type uses a two-mask optical lithography process to create asymmetric ohmic and Schottky contacts. For the symmetric ohmic contacts, at a voltage bias of 1?V across the device, we observed a 29-fold increase in current in comparison to dark current when the NWs were photo-excited by a 400?nm light-emitting diode (LED) at 0.15?mW?cm(-2) with a relaxation time constant (τ) ranging from 50 to 555?s. For the asymmetric ohmic and Schottky contacts under 400?nm excitation, τ is measured between 0.5 and 1.4?s over varying time internals, which is ～2 orders of magnitude faster than the devices using symmetric ohmic contacts.     

Stable p-type conduction from Sb-decorated head-to-head basal plane inversion domain boundaries in ZnO nanowires

We report that Sb-decorated head-to-head (H-H) basal plane inversion domain boundaries (b-IDBs) lead to stable p-type conduction in Sb-doped ZnO nanowires (NWs) due to Sb and O codoping. Aberration-corrected Z-contrast scanning transmission electron microscopy shows that all of the Sb in the NWs is incorporated into H-H b-IDBs just under the (0001) NW growth surfaces and the (0001) bottom facets of interior voids. Density functional theory calculations show that the extra basal plane of O per H-H b-IDB makes them electron acceptors. NWs containing these defects exhibited stable p-type behavior in a single NW FET over 18 months. This new mechanism for p-type conduction in ZnO offers the potential of ZnO NW based p-n homojunction devices.     

Structural and optical properties of individual GaP/ZnO core–shell nanowires

Structural and optical properties of ZnO–GaP core–shell nanowires were studied by means of electron microscopy and microphotoluminescence. A thin ZnO shell layer was deposited by RF sputtering on GaP nanowires, which were grown on GaP (111)B substrates under vapour–liquid–solid mode by MOVPE. The SEM and TEM characterization showed that the ZnO shells fully covered the surface of the NWs from top to bottom. Each GaP NW core is composed of many well-defined twinned segments with the planes of twinning oriented in perpendicular to the growth direction. This was contradicted in kinked GaP NWs: their growth direction was initially perpendicular to the twinning planes, but once the NW had kinked, it changed to lie within the twinning planes. The ZnO shell deposited on the GaP core has a columnar morphology. The columns are inclined at a positive angle close to 70° with respect to the GaP growth axis. All observed columns were tilted at this angle to the growth direction. Micro-photoluminescence study showed that thermal annealing improved the quality of the ZnO crystallographic structure; the annealing made observable the photoluminescence peak related to the band-to-band transition in ZnO.     

Quantum confinement and electroluminescence in ultrathin silicon nanowires fabricated by a maskless etching technique

We present a novel approach for the direct synthesis of ultrathin Si nanowires (NWs) exhibiting room temperature light emission. The synthesis is based on a wet etching process assisted by a metal thin film. The thickness-dependent morphology of the metal layer produces uncovered nanometer-size regions which act as precursor sites for NW formation. The process is cheap, fast, maskless and compatible with Si technology. Very dense arrays of long (several micrometers) and small (diameter of 5-9?nm) NWs have been synthesized. An efficient room temperature luminescence, visible with the naked eye, is observed when NWs are optically excited, exhibiting a blue-shift with decreasing NW size in agreement with quantum confinement effects. A prototype device based on Si NWs has been fabricated showing a strong and stable electroluminescence at low voltages. The relevance and the perspectives of the reported results are discussed, opening the route toward novel applications of Si NWs.     

p-Type ZnO nanowire arrays

Well-aligned ZnO nanowire (NW) arrays with durable and reproducible p-type conductivity were synthesized on alpha-sapphire substrates by using N2O as a dopant source via vapor-liquid-solid growth. The nitrogen-doped ZnO NWs are single-crystalline and grown predominantly along the [110] direction, in contrast to the [001] direction of undoped ZnO NWs. Electrical transport measurements reveal that the nondoped ZnO NWs exhibit n-type conductivity, whereas the nitrogen-doped ZnO NWs show compensated highly resistive n-type and finally p-type conductivity upon increasing N2O ratio in the reaction atmosphere. The electrical properties of p-type ZnO NWs are stable and reproducible with a hole concentration of (1-2) x 10(18) cm(-3) and a field-effect mobility of 10-17 cm2 V(-2) s(-1). Surface adsorptions have a significant effect on the transport properties of NWs. Temperature-dependent PL spectra of N-doped ZnO NWs show acceptor-bound-exciton emission, which corroborates the p-type conductivity. The realization of p-type ZnO NWs with durable and controlled transport properties is important for fabrication of nanoscale electronic and optoelectronic devices.