Optical properties of ZnO nanowire arrays electrodeposited on n- and p-type Si(1 1 1): Effects of thermal annealing

Electrodeposition is a low temperature and low cost growth method of high quality nanostructured active materials for optoelectronic devices. We report the electrochemical preparation of ZnO nanorod/nanowire arrays on n-Si(1 1 1) and p-Si(1 1 1). The effects of thermal annealing and type of substrates on the optical properties of ZnO nanowires electroplated on silicon (1 1 1) substrate are reported. We fabricated ZnO nanowires/p-Si structure that exhibits a strong UV photoluminescence emission and a negligible visible emission. This UV photoluminescence emission proves to be strongly influenced by the thermal annealing at 150-800 °C. Photo-detectors have been fabricated based on the ZnO nanowires/p-Si heterojunction.     

Synthesis and characterization of ZnO nanowires for nanosensor applications

In this paper we report the synthesis of ZnO nanowires via chemical vapor deposition (CVD) at 650 °C. It will be shown that these nanowires are suitable for sensing applications. ZnO nanowires were grown with diameters ranging from 50 to 200 nm depending on the substrate position in a CVD synthesis reactor and the growth regimes. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Raman spectroscopy (RS) have been used to characterize the ZnO nanowires. To investigate the suitability of the CVD synthesized ZnO nanowires for gas sensing applications, a single ZnO nanowire device (50 nm in diameter) was fabricated using a focused ion beam (FIB). The response to H₂ of a gas nanosensor based on an individual ZnO nanowire is also reported.     

Layer-by-layer assembly synthesis of ZnO/SnO2 composite nanowire arrays as high-performance anode for lithium-ion batteries

A layer-by-layer approach has been developed to synthesize ZnO/SnO₂ composite nanowire arrays on copper substrate. ZnO nanowire arrays have been first prepared on copper substrate through seed-assisted method, and then, the surface of ZnO nanowires have been modified by the polyelectrolyte. After oxidation-reduction reaction, SnO₂ layer has been deposited onto the surface of ZnO nanowires. The as-synthesized ZnO/SnO₂ composite nanowire arrays have been applied as anode for lithium-ion batteries, which show high reversible capacity and good cycling stability compared to pure ZnO nanowire arrays and SnO₂ nanoparticles. It is believed that the improved performance may be attributed to the high capacity of SnO₂ and the good cycling stability of the array structure on current collector.     

Ordered ZnO/AZO/PAM nanowire arrays prepared by seed-layer-assisted electrochemical deposition

An Al-doped ZnO (AZO) seed layer is prepared on the back side of a porous alumina membrane (PAM) substrate by spin coating followed by annealing in a vacuum at 400 °C. Zinc oxide in ordered arrays mediated by a high aspect ratio and an ordered pore array of AZO/PAM is synthesized. The ZnO nanowire array is prepared via a 3-electrode electrochemical deposition process using ZnSO₄ and H₂O₂ solutions at a potential of − 1 V (versus saturated calomel electrode) and temperatures of 65 and 80 °C. The microstructure and chemical composition of the AZO seed layer and ZnO/AZO/PAM nanowire arrays are characterized by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and energy-dispersive X-ray spectroscopy (EDS). Results indicate that the ZnO/AZO/PAM nanowire arrays were assembled in the nanochannel of the porous alumina template with diameters of 110–140 nm. The crystallinity of the ZnO nanowires depends on the AZO seed layer during the annealing process. The nucleation and growth process of ZnO/AZO/PAM nanowires are interpreted by the seed-layer-assisted growth mechanism.     

Improving the NH(3) gas sensitivity of ZnO nanowire sensors by reducing the carrier concentration

We report a method to improve the sensitivity of a zinc oxide (ZnO) nanowire gas sensor towards ammonia (NH(3)) without the use of catalyst nanoparticles on the nanowire surface. This improvement is achieved by lowering the nominal carrier concentration in the as-grown ZnO nanowires. The carrier concentration in the as-grown ZnO nanowires can be tuned by treating these nanowires to either an oxidizing gas plasma or a reducing gas plasma, as observed from the measured current-voltage (I-V) characteristics response. We demonstrate that a ZnO nanowire sensor device that has been subjected to oxygen plasma treatment, thereby having a reduced carrier concentration, exhibits a sensitivity towards 0.75% NH(3) gas that is improved by approximately four times. The origin of this gas sensitivity improvement is discussed based on x-ray photoelectron spectroscopy analysis results of the plasma-treated ZnO nanowires.     

Superior Functionality by Design: Selective Ozone Sensing Realized by Rationally Constructed High‐Index ZnO Surfaces

A new technique is reported for the transformation of smooth nonpolar ZnO nanowire surfaces to zigzagged high‐index polar surfaces using polycrystalline ZnO thin films deposited by atomic layer deposition (ALD). The c‐axis‐oriented ZnO nanowires with smooth nonpolar surfaces are fabricated using vapor deposition method and subsequently coated by ALD with a ZnO particulate thin film. The synthesized ZnO–ZnO core–shell nanostructures are annealed at 800 °C to transform the smooth ZnO nanowires to zigzagged nanowires with high‐index polar surfaces. Ozone sensing response is compared for all three types of fabricated nanowire morphologies, namely nanowires with smooth surfaces, ZnO–ZnO core–shell nanowires, and zigzagged ZnO nanowires to determine the role of crystallographic surface planes on gas response. While the smooth and core–shell nanowires are largely non‐responsive to varying O₃ concentrations in the experiments, zigzagged nanowires show a significantly higher sensitivity (ppb level) owing to inherent defect‐rich high‐index polar surfaces.     

The characteristic of the ZnO nanowire morphology grown by the hydrothermal method on various surface-treated seed layers

ZnO nanowires with various density and diameters were obtained by altering the wetting properties of aluminum doped ZnO (AZO) seed layers. AZO seed layers deposited on glass substrates were treated by inductor coupled plasmas (ICP) or atmospheric pressure plasma (APP) systems in order to control wettability before ZnO nanowire growth. Morphology of ZnO nanowires grown by the hydrothermal method was influenced by wettability of AZO seed layers. Our investigation shows that the diameter of ZnO nanowire increases and the length of ZnO nanowire decreases when the contact angle on the AZO seed layer is decreased. As a result, we confirmed that the morphology of ZnO nanowires could be easily controlled by surface treatment of seed layers with the plasma system.     

The Piezotronic Effect of Zinc Oxide Nanowires Studied by In Situ TEM

Piezotronics is a new field integrating piezoelectric effect into nanoelectronics, which has attracted much attention for the fundamental research and potential applications. In this paper, the piezotronic effect of zinc oxide (ZnO) nanowires, including the response of the electrical transport and photoconducting behaviors on the nanowire bending, has been investigated by in situ transmission electron microscopy (TEM), where the crystal structure of ZnO nanowires were simultaneously imaged. Serials of consecutively recorded current‐voltage (I–V) curves along with an increase of nanowire bending show the striking effect of bending on their electrical behavior. With increasing the nanowire bending, the photocurrent of ZnO nanowire under ultraviolet illumination (UV) drops dramatically and the photo response time becomes much shorter. In addition, the dynamic nanomechanics of ZnO nanowires were studied inside TEM. These phenomena could be attributed to the piezoelectric effect of ZnO nanowires, and they suggest the potential applications of ZnO nanowires on piezotronic devices.     

PABA-assisted hydrothermal fabrication of W18O49 nanowire networks and its transition to WO3 for photocatalytic degradation of methylene blue

W₁₈O₄₉ nanowire networks have been fabricated by a facile hydrothermal method. In this method, p-aminobenzoic acid (PABA) was used as an assistant agent to control the morphology transformation. W₁₈O₄₉ and its products annealed at different temperature were characterized by XRD, SEM, TEM, UV–vis absorption spectroscopy, XPS, TGA, and FTIR. Formation mechanism and thermal stability of W₁₈O₄₉ nanowire networks were studied in detail. The experiment data showed that PABA played an important role in the induced crystal growth of W₁₈O₄₉ nanowires along [0?1?0] axis. In transformation, the structure of samples was controlled: from irregular particles to nanowire networks. W₁₈O₄₉ nanowire networks were annealed at different temperature. The nanowire networks collapsed at 450?°C, while WO₃ nanocrystals were obtained. The W₁₈O₄₉ nanowire networks annealed at 400?°C have a superior photocatalytic performance to degrade methylene blue and its specific surface area was up to 147?m²?g^?1.     

反应源温度对ZnO纳米线阵列定向性及发光性能的影响

以Au薄膜为催化剂、ZnO与碳混合粉末为反应源,采用碳热还原法在单晶Si衬底上制备了ZnO纳米线阵列.通过扫描电子显微镜( SEM)、X射线衍射仪(XRD)、荧光分光光度计对样品的表征,研究了反应源温度对ZnO纳米线阵列的定向性和光致发光性能的影响.样品在源温度920℃条件下沿(002)方向择优生长,定向性最好,温度过低不利于ZnO纳米线阵列密集生长,而温度过高导致Zn原子二次蒸发,因而也不利于纳米线阵列的定向和择优生长;样品在源温度880℃有最强的近紫外带边发射,表明温度过高和过低都不利于ZnO晶体结构的优化;由于ZnO纳米线在缺氧氛围下生长,氧空位是缺陷存在的主要形式,因此所有样品都有较强的绿光发射.温度升高导致纳米线生长速度提高而增加了氧空位缺陷数量,从而使样品绿峰强度增强并在源温度920℃时达最大值,但温度的进一步升高可导致ZnO纳米线表面Zn元素的蒸发而降低氧空位缺陷的数量,从而抑制绿峰强度.     

Effects of post annealing temperature on formation of alumina core shell on zinc oxide nanowire: optoelectronic properties and dye sensitized solar cell applications

Alumina coated zinc oxide (ZnO) nanowires were synthesized through the combination of hydrothermal growth and sol–gel deposition method. The effects of post annealing temperature on structural and optoelectronic properties of the deposited samples were evaluated using scanning electron microscopy, X-ray diffraction, energy dispersive spectroscopy, photoluminescence spectroscopy and Raman spectroscopy. It was found that the ZnO nanowire can be used as template for further functionalization. As a demonstration, dye sensitized solar cells were fabricated with the alumina coated ZnO nanowires.     

Fabrication and characterization of a composite ZnO semiconductor as electron transporting layer in dye-sensitized solar cells

ZnO nanocomposites involving nanowires and nanoparticles with a thickness of 4 μm were grown by chemical bath deposition and used as electron transporting layer in dye-sensitized solar cells (DSSCs). The growth of ZnO nanowires was initially achieved in a zinc nitrate and hexamethylenetetramine aqueous solution on a fluorine-doped tin oxide thin film seeded with ZnO nanoparticles. Subsequently, layered hydroxide zinc acetate (LHZA) nanoparticles were deposited on the nanowires by dip coating in a zinc acetate methanolic solution. A relatively conformal deposit of nanoparticles all along the nanowires was revealed by scanning and transmission electron microscopy. It is shown by X-ray diffraction measurements that a subsequent annealing convert the LHZA nanoparticles into ZnO nanoparticles. The resulting DSSCs present a short circuit current density almost three times higher when the ZnO nanowire interstices were filled with ZnO nanoparticles, which is due to a higher dye loading for a constant device thickness. This is correlated with a very high specific surface area in ZnO nanocomposites, which is 250 times larger than the geometrical surface area. Although a decrease in both the open circuit voltage and the fill factor was shown by electrochemical impedance spectroscopy owing to an increase in electron radiative and nonradiative recombinations, the efficiency of ZnO nanocomposite-based-DSSCs was on average 1.75%, which is 70% higher than for single ZnO nanowire-based-DSSCs.     

Influence of seed layers on the vertical growth of ZnO nanowires

We synthesized vertically aligned ZnO nanowires on SiO₂ wafer <100> using the Au, ZnO and Au/ZnO seed layers through the physical vapor deposition process. The growth direction of ZnO nanowire was controlled by using the three different seed layers. From the XRD results, we observed the highest intensity of the (002) peak on the Au/ZnO seed layer among the three seed layers. The SEM images show that all of the ZnO nanowires have an average diameter of about 100 ~ 200 nm and a length of about 5 μm, and the nanowires grown on the Au/ZnO seed layer are oriented the most perpendicularly to the substrate surface. From the PL analysis, we observed that the intensity of broad emissions at 400-600 nm relating the green emission for the ZnO nanowires on the Au/ZnO seed layer was much weaker than that for the ZnO nanowires on the ZnO seed layer. The experiment results indicate that the selection of seed layers is important to grow nanowires vertically for the application of nanoscale devices.     

Synthesis of ZnO nanowires by the hydrothermal method,using sol–gel prepared ZnO seed films

Zinc oxide (ZnO) nanowires with various morphologies are synthesized by the hydrothermal method on silicon substrates coated with ZnO thin films. The ZnO films are used as the seed layer and are prepared using the sol–gel technique. Experimental results demonstrate that the synthesis of ZnO nanowires is dependent on the crystalline properties of the ZnO seed-layer films. Sol concentration is the controlled parameter for the preparation of ZnO seed-layer films in this study. The ZnO films are found to have the hexagonal wurtzite structure with highly preferred growth along the c-axis at suitable sol concentrations. The vertically aligned ZnO nanowire arrays on the substrates are believed to be the result of the epitaxial growth of the ZnO seed layer. Scanning electron microscopy shows that nanowires with uniform distribution in length, diameter, and density are obtained. X-ray diffraction patterns clearly reveal that the ZnO nanowires are primarily grown along the c-axis direction. Transmission electron microscopy and selected-area electron diffraction measurements show that the nanowires have good crystalline properties. The well-aligned and high surface areas of the ZnO nanowires make them a potential candidate for applications in solar cells, field emission devices, and ultra-sensitive gas sensors.     

Controlled growth of zinc nanowires

Zinc nanowires have been synthesized by heating a mixture of boron and zinc oxide (ZnO) powders at 1050 °C under a nitrogen atmosphere. The influences of the gas flow rate and the substrate character on the nanowire formation were investigated. It was found that higher-flow rate of gas led to the formation of thinner nanowires; while lower-flow rate of gas produced thicker nanowires and even particles due to the higher partial pressure of Zn vapor in this case. Zn nanowires can be produced on alumina and quartz substrates, but not on a stainless-steel substrate under the same or different synthetic conditions. Photoluminescence measurements were conducted on Zn nanowires and particles and weak emission bands at 482 and 493 nm were observed, which may be contributed by the thin ZnO film on the nanowire surface.     

Effect of surface morphology of metallic zinc films deposited by ion beam sputter deposition on the formation of ZnO nanowires

Metallic zinc film with various surface roughnesses was deposited on Si (100) substrates by ion beam sputter deposition utilizing beam energies at 8, 12 and 16 keV. The surface roughness of the metallic zinc film increased as ion beam energy increased and was found to act as a crucial factor for the formation of ZnO nanowires by subsequent thermal oxidation. ZnO nanowires with diameters of ∼30 nm and average length of ∼1 μm were obtained from 12 to 16 keV ion beam deposited samples while no ZnO nanowires were found on 8 keV ion beam deposited samples. Photoluminescence study of ZnO nanowires exhibits a strong UV emission at 377.2 nm (3.287 eV) with a full-width at half maximum of 95.0 meV and negligible defect related deep level emission. The ZnO nanowires are grown along the [110] direction and the growth mechanism is likely due to a solid state based-up diffusion process. Field-emission measurement shows a turn-on field of 7.9 MV/m and a field enhancement factor β of 691 is achieved.     

ZnO纳米线阵列修饰对材料表面浸润性调控

采用溶胶-凝胶法制备了ZnO薄膜,利用溶剂热沉积法获得大面积均匀ZnO纳米线阵列。通过对水在ZnO材料表面的浸润性研究,发现薄膜材料表面的粗糙度对ZnO膜亲水性有增强作用,而周期性ZnO阵列微结构表面可以实现其疏水性质增强效果。同时从理论上分析了这两种现象的物理机制,讨论了空气填隙对ZnO纳米线阵列表面的浸润性质的敏感性。制备出ZnO纳米线阵列的表观接触角约为103°,具有较强的疏水性质,可为进一步的ZnO光流控研究提供实验基础。     

Synthesis of ZnO nanowire array film on Mg doped gallium nitride substrate

ZnO nanowire array films, composed of well aligned ZnO nanowires ～200?nm in diameter and 1?μm in length, were successfully synthesised on Mg doped gallium nitride by hydrothermal method. In addition, the films possess quite flatten surface. In the synthesised process, there was no catalyst that had been used. Growth conditions were comprehensively discussed in the process of aqueous solution method. It was found that the length of ZnO nanowires and the thickness of the film could be tunable by altering solution concentration and growth time. Such ZnO film assembled with vertically aligned nanowire may have potential applications as UV light emitting diodes.     

Effect of surface morphology of metallic zinc films deposited by ion beam sputter deposition on the formation of ZnO nanowires

Metallic zinc film with various surface roughnesses was deposited on Si (100) substrates by ion beam sputter deposition utilizing beam energies at 8, 12 and 16 keV. The surface roughness of the metallic zinc film increased as ion beam energy increased and was found to act as a crucial factor for the formation of ZnO nanowires by subsequent thermal oxidation. ZnO nanowires with diameters of ∼30 nm and average length of ∼1 μm were obtained from 12 to 16 keV ion beam deposited samples while no ZnO nanowires were found on 8 keV ion beam deposited samples. Photoluminescence study of ZnO nanowires exhibits a strong UV emission at 377.2 nm (3.287 eV) with a full-width at half maximum of 95.0 meV and negligible defect related deep level emission. The ZnO nanowires are grown along the [110] direction and the growth mechanism is likely due to a solid state based-up diffusion process. Field-emission measurement shows a turn-on field of 7.9 MV/m and a field enhancement factor β of 691 is achieved.     

High efficiency dye-sensitized solar cells based on three-dimensional multilayered ZnO nanowire arrays with "caterpillar-like" structure

A 3D ZnO nanowire-based dye-sensitized solar cell (DSSC) with unique "caterpillar-like" structure was designed. Because of the significant improvement of the total ZnO nanowire surface area, the amount of light absorption was substantially increased. This increase in the light harvesting efficiency enables us to achieve an overall power conversion efficiency as high as 5.20%, which is the highest reported value to date for ZnO nanowire-based DSSCs. A branched-multilayered design of ZnO nanowire arrays grown from ZnO nanofiber seed layers proves to be very successful in fabricating 3D ZnO nanowire arrays. Practically, electrospun ZnO nanowires were used as the seeds in multilayer growth of ZnO nanowire arrays with a unique "caterpillar-like" structure. This unique structure significantly enhances the surface area of the ZnO nanowire arrays, leading to higher short-circuit currents. Additionally, this design resulted in closer spacing between the nanowires and more direct conduction pathways for electron transfer. Thus, the open-circuit voltage was so significantly improved as a direct result of the reduction in electron recombination.