Growth of ZnO nanodisk, nanospindles and nanoflowers for gas sensor: pH dependency

Suitable morphology for fast electron transportation is a crucial requirement for the fabrication of gas sensor application. Highly oriented and well defined zinc oxide (ZnO) nano/micro-scale structures are grown on the glass substrates using aqueous chemical route. The grown nanostructures have been characterized by X-ray diffraction pattern (XRD), scanning electron microscope (SEM) and optical absorption techniques. The SEM micrographs revealed the formation of disk, rod, spindle and flower-like morphologies at different pH values ranging from 5 to 10. The grown nanostructures were employed for acetone gas-sensing measurement. It is observed that the sensors based on nanoflowers showed higher response (95%) for acetone gas at 325 °C. The high acetone gas sensitivity of ZnO nanoflowers can be attributed to the surface morphology. Moreover, nanoflower-like structure exhibits the fast response and recovery.     

Template-free hydrothermal synthesis of ZnO microrods for gas sensor application

Zinc oxide microrods with controlled diameter were prepared without the addition of template and additive by a simple hydrothermal route only using Zn(CH₃COO)₂·2H₂O as a precursor. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and electron diffraction (ED). The crystal structure of prepared ZnO microrods is hexagonal phase polycrystalline with zincite structure. With the increase of the precursor concentration from 0.05 M to 0.6 M, the diameter of the ZnO microrods increased from 1 μm to 5 μm. A localized oriented attachment mechanism was prepared to account for the formation of ZnO microrods. The gas-sensing performance experiments indicated that the prepared ZnO microrods exhibited highly sensitive, selective gas-sensing properties, and good stability to acetone vapor. The response and recovery time of ZnO-based gas sensor to 100 ppm acetone vapor are 12 s and 18 s, respectively. The mechanism of the ZnO-based sensor was investigated.     

多孔ZnO微米球的制备及其优异的丙酮敏感特性

以六水合硝酸锌、尿素为原料,以六亚甲基四胺为表面活性剂,利用水热法合成了多孔氧化锌微米球.通过X射线衍射仪、扫描电子显微镜和吸附仪对样品的结构、形貌、比表面积和孔径进行了表征.利用所得多孔微米球氧化锌制备了气敏元件,并对其气敏特性进行了测试.结果表明:在280℃的工作温度下,表面多孔氧化锌微米球气敏元件对50 ppm的丙酮气体的灵敏度为26.8,响应时间和恢复时间分别约为4 s和10 s,并具有良好的选择性.     

Sensitivity enhancement of AZO-based ethanol sensor decorated by Au nano-islands

Detecting the hazardous gases for monitoring air pollution and medical diagnosis make highly sensitive gas sensors appeal to many researches. In this paper, benefiting from unique properties of noble metals, Al-doped ZnO based Ethanol sensors were fabricated and characterized in three structures including Al: ZnO thin film, Silver and Gold nano-islands on Al: ZnO thin film. The Silver and Gold thin films turn to nano-islands after a simple annealing process. The XRD analysis of the sputtered Al: ZnO layer indicates the wurtzite crystal structure of the layer with a peak at (002) plane. Moreover, the sensitivity study reveals that Nano-islands of noble metals substantially affects the sensitivity of the sensors. The decorated Gold nano-island Al: ZnO Ethanol sensor has the highest response showing an amount of 45. The response of Al: ZnO and Silver decorated Al: ZnO sensors are virtually identical to all concentrations of Ethanol, whereas the Al: ZnO gas sensor with Gold nano-islands has the substantial sensitivity for different concentrations. In addition, the response times of the sensors are 85, 70 and 90 s for Al: ZnO, Al: ZnO with Ag islands and Al: ZnO decorated by Au islands, respectively. The recovery time of Al: ZnO sensor decorated by Au islands is about 23s, while the recovery time of the Al: ZnO and Al: ZnO decorated by Silver islands are 360 and 370s, respectively. Hence, the simple annealing process on the sputtered gas sensor with a thin layer of Gold makes nano-islands on the sensor which elevates the performance of Ethanol sensing due to the high sensitivity and sensitivity of the sensor.     

Laser-assisted generation of gold nanoparticles and nanostructures in liquid and their plasmonic luminescence

Nanoparticles (NPs) and surface nanostructures (NS) are produced via laser ablation of a bulk gold target in liquid using second harmonics of 10 ps Nd:YAG laser (532 nm) with repetition rate of 50 kHz. The morphology and plasmon photoluminescence (PL) properties of obtained nanoscale objects are described. Transmission electron microscopy and field emission scanning electron microscopy are used for morphology characterization of NPs and NS, respectively. Plasmon PL of both gold NPs and NS is experimentally studied using the third harmonics of the Nd:YAG picosecond laser (355 nm) as a pump. The wavelength of intensity maximum of PL of Au NPs colloidal solution virtually coincides with the position of Au NPs plasmon absorption peak. Real-time excitation of both plasmon PL and Raman scattering of surrounding liquid by picosecond laser pulses in aqueous colloidal solution is also investigated. The efficient cross section of plasmon PL of Au NPs colloid is evaluated using Raman scattering of water as a comparative parameter. The results are in good agreement with values obtained in previous works. Plasmon PL from self-organized NS on the Au surface produced via laser ablation is observed for the first time. Its spectrum is compared to PL spectra of both aqueous colloidal solutions of NPs and of NPs deposited on a Si wafer. The obtained experimental data are discussed with reference to the band structure of bulk Au.     

Chronic exposure to zinc oxide nanoparticles increases ischemic-reperfusion injuries in isolated rat hearts

The use of zinc oxide nanoparticles (ZnO NPs) in numerous products is increasing, although possible negative implications of their long-term consumption are not known yet. Our aim was to evaluate the chronic, 6-week oral exposure to two different concentrations of ZnO NPs on isolated rat hearts exposed to ischemic-reperfusion injury and on small intestine morphology. Wistar rats of both sexes (n = 18) were randomly divided into three groups: (1) 4 mg/kg ZnO NPs, (2) 40 mg/kg ZnO NPs, and (3) control. After 6 weeks of treatment, the hearts were isolated, the left ventricular pressure (LVP), the coronary flow (CF), the duration of arrhythmias and the lactate dehydrogenase release rate (LDH) were measured. A histological investigation of the small intestine was performed. Chronic exposure to ZnO NPs acted cardiotoxic dose-dependently. ZnO NPs in dosage 40 mg/kg maximally decreased LVP (3.3-fold) and CF (2.5-fold) and increased the duration of ventricular tachycardia (all P < 0.01) compared to control, whereas ZnO NPs in dosage 4 mg/kg acted less cardiotoxic. Goblet cells in the small intestine epithelium of rats, treated with 40 mg ZnO NPs/kg, were enlarged, swollen and numerous, the intestinal epithelium width was increased. Unexpectedly, ZnO NPs in both dosages significantly decreased LDH. A 6-week oral exposure to ZnO NPs dose-dependently increased heart injuries and caused irritation of the intestinal mucosa. A prolonged exposure to ZnO NPs might cause functional damage to the heart even with exposures to the recommended daily doses, which should be tested in future studies.     

A rapid synthesis/growth process producing massive ZnO nanowires for humidity and gas sensing

We report a rapid and simple process to massively synthesize/grow ZnO nanowires capable of manufacturing massive humidity/gas sensors. The process utilizing a chemical solution deposition with an annealing process (heating in vacuum without gas) is capable of producing ZnO nanowires within an hour. Through depositing the ZnO nanowires on the top of a Pt-interdigitated-electrode/SiO₂/Si-Wafer, a humidity/gas-hybrid sensor is fabricated. The humidity sensitivity (i.e., ratio of the electrical resistance of the sensor at 11–95 % relative humidity level) is approximately 10⁴. The response and recovery time with the humidity changing from 11 to 95 % directly and reversely is 6 and 10 s, respectively. The gas sensitivity (i.e., ratio of electrical resistance of the sensor under the air to vaporized ethanol) is increased from 2 to 56 when the concentration of the ethanol is increased from 40 to 600 ppm. Both the response and recovery times are less than 15 s for the gas sensor. These results show the sensor utilizing the nanowires exhibits excellent humidity and gas sensing.     

ZnO nanoparticle-modified ionic liquid-carbon paste electrodefor voltammetric determination of folic acid in food and pharmaceutical samples

In this work, a ZnO/nanoparticles (NPs) modified carbon ionic liquid paste electrode (ZnO/NP/CILPE) was fabricated and used to investigate the electrochemical behavior of folic acid. ZnO/NP/CILPE was prepared by mixing hydrophilic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mim]-[PF₆])), ZnO/NPs, graphite powder, and liquid paraffin together. The fabricated ZnO/NP/CILPE showed great electrocatalytic ability to the oxidation of folic acid, and an irreversible oxidation peak appeared at 0.75 V (vs. Ag/AgCl) with improved peak current. Under the optimized conditions of pH 9.0, the plot of peak current vs. folic acid concentration consisted of two linear segments with slopes of 1.776and 0.033 μA/μM in the concentration ranges of 0.05–1.5 μM and 1.5–550.0 μM, respectively. The detection limit was 0.01 μM (3σ). The proposed sensor was successfully applied for the determination of folic acid in fortified food and pharmaceutical samples.     

One-step synthesis of flower-like Au-ZnO microstructures at room temperature and their photocatalytic properties

In this paper, 3D flower-like Au-ZnO microstructures with controlled morphology and dimensions were synthesized by a facile one-step aqueous solution route at room temperature, and the photocatalytic properties of these structures were investigated. The as-prepared flower-like Au-ZnO structures with a diameter of about 3 μm consisted of many ZnO nanosheets which interacted with each other. These nanosheets, which were successfully decorated by Au NPs, showed an average thickness of 10 nm and a single-crystalline structure with {2-1-10} planar surfaces. The growth process of Au-ZnO structures and the effects of trisodium citrate on the nucleation and growth of ZnO were investigated. The formation of Au NPs in this experiment was discussed too. The Au-ZnO structures showed higher photocatalytic activity than that of pure ZnO.     

Optical and room temperature sensing properties of highly oxygen deficient flower-like ZnO nanostructures

Oxygen deficient zinc oxide (ZnO) thin films were deposited electrochemically on glass substrates which are pre-sputtered with pure zinc (Zn) metal. Well-arranged flower-like nanostructures are observed from the SEM micrographs. The purity and crystallinity of the deposited films were confirmed from X-ray diffraction studies supported by Raman studies. The broad and intense defect induced green emission confirms the high oxygen deficiency in the nanostructures. The flower-like structures as well as the oxygen defects present in the system are indeed very suitable for gas and chemical sensing applications. These films were used for room temperature sensing of three different chemicals viz. acetone, ethanol and ammonia. The sensor was found to be insensitive to the change in different concentrations of acetone while it was found to be sensitive to different concentrations of ethanol and ammonia. The sensor is most suitable for sensing ammonia at room temperature.     

Low-temperature growth and ethanol-sensing characteristics of quasi-one-dimensional ZnO nanostructures

ZnO nanorods, nanobelts, nanowires, and tetrapod nanowires were synthesized via thermal evaporation of Zn powder at temperatures in the range 550-600 °C under flow of Ar or Ar/O₂ as carrier gas. Uniform ZnO nanowires with diameter 15-25 nm and tetrapod nanowires with diameter 30-50 nm were obtained by strictly controlling the evaporation process. Our experimental results revealed that the concentration of O₂ in the carrier gas was a key factor to control the morphology of ZnO nanostructures. The gas sensors fabricated from quasi-one-dimensional (Q1D) ZnO nanostructures exhibited a good performance. The sensor response to 500 ppm ethanol was up to about 5.3 at the operating temperature 300 °C. Both response and recovery times were less than 20 s. The gas-sensing mechanism of the ZnO nanostructures is also discussed and their potential application is indicated accordingly.     

Plasmonic enhancement of optical absorption of UV radiation by Au nanoparticles dispersed on ZnO thin film

Ultraviolet photoconductivity in sol gel-derived ZnO thin film loaded with gold (Au) nanoparticle (NPs) is investigated. Au-NPs loaded ZnO thin film (Au-NPs/ZnO) is found to exhibit high photoconducting gain (K) of about 4.12 × 10³ as compared to the bare ZnO thin film-based photodetector (4.9 × 10¹). The enhanced photoconductive gain of Au-NPs/ZnO detector has been achieved due to simultaneous lowering of dark current which occurs due to Schottky barrier effect originated after dispersing the Au NPs on the surface of ZnO thin film. The enhancement in photocurrent upon UV illumination is due to trapping of UV radiation via plasmonic effect caused by Au-NPs and subsequently coupling of absorbed light with the optical modes of underlying semiconducting ZnO surface.     

Highly sensitive breath sensor based on sonochemically synthesized cobalt-doped zinc oxide spherical beads

In this study, we introduce cobalt (Co)-doped zinc oxide (ZnO) spherical beads (SBs), synthesized using a sonochemical process, and their utilization for an acetone sensor that can be applied to an exhalation diagnostic device. The sonochemically synthezied Co-doped ZnO SBs were polycrystalline phases with sizes of several hundred nanometers formed by the aggregation of ZnO nanocrystals. As the Co doping concentration increased, the amount of substitutionally doped Co²⁺ in the ZnO nanocrystals increased, and we observed that the fraction of Co³⁺ in the Co-doped ZnO SBs increased while the fraction of oxygen vacancies decreased. At an optimal Co-doping concentration of 2 wt%, the sensor operating temperature decreased from 300 to 250 °C, response to 1 ppm acetone improved from 3.3 to 7.9, and minimum acetone detection concentration was measured at 43 ppb (response, 1.75). These enhancements are attributed to the catalytic role of Co³⁺ in acetone oxidation. Finally, a sensor fabricated using 2 wt% Co-doped ZnO SBs was installed in a commercially available exhalation diagnostic device to successfully measure the concentration of acetone in 1 ml of exhaled air from a healthy adult, returning a value of 0.44 ppm.     

First-principles studies on the Au surfactant on polar ZnO surfaces

The surfactant effect of Au in ZnO nanostructures growth is studied using first-principles slab calculations based on density functional theory. The atomic structure and electronic properties of one monolayer of Au atoms on polar ZnO surfaces are examined. It is found that (1) one monolayer (ML) of Au capping layer on the ZnO polar surfaces may modify the growing properties of ZnO nanostructures by enhancing the binding energy by 0.41 eV/atom for Zn adsorption on the polar surfaces; (2) the Au adlayer on the polar ZnO surfaces seems more active for the adsorption of Zn atoms, which may be at the very heart of the effect that Au acts as catalyst for the growth of the ZnO nanostructures; and (3) total energy calculations show that the gold on-top geometry is energetically favorable than the gold diffused geometry, which may be useful to understand the phenomenon that Au particles are only found at the end of ZnO nanostructures during the growth process.     

Pd nanoparticle-mediated acetone sensing performance improvement of SnO2 substrate: A combined DFT and experimental study

The article presents a combined theoretical and experimental study attempting to show how Pd nanoparticles (NPs) loading onto SnO₂ substrate improves the acetone gas sensing performance. Pristine nanostructured SnO₂ and Pd nanoparticles (Pd NPs) loaded SnO₂ substrates have been prepared, characterized, and their acetone sensing performances have been measured. Experimental measurements have shown that Pd NP loading onto SnO₂ suppresses the interfering effects of ethanol, water vapors, etc., and enhances the acetone sensor response, reversibility, response/recovery speeds, and signal-to-noise ratio. Various parameters like the adsorption energy, HOMO–LUMO energy gap, charge distribution, polarizability change, electrophilicity index, global hardness, etc., of several model systems, have been computed by using DFT. The computed parameters have been correlated with the conductivity, local reactivity, sensor response and selectivity, response/recovery times, etc., of the systems to understand the molecular-level effects of the Pd NP loading onto the SnO₂ on the gas sensing process.     

Nanostructure size evolution during Au-catalysed growth by carbo-thermal evaporation of well-aligned ZnO nanowires on (100)Si

We report the structural and morphological properties of well-aligned ZnO nanowires grown at 750 °C on Au-deposited and annealed (100)Si substrates using carbo-thermal evaporation. As-grown nanowires are made of wurtzite ZnO, have cylindrical shape and carry droplet-like nanoparticles (NPs) at their tips, as expected for vapour–liquid–solid (VLS) growth. Grazing incidence X-ray diffraction measurements demonstrate that the NPs are made of pure fcc Au. No secondary Au/Zn alloy phases were detected. Bragg diffraction patterns confirmed that the nanowires were grown with their crystal c-axes parallel to the [100] direction of Si (i.e. normal to the substrate surface), while Au NPs are mostly (111)-oriented. The diameter distribution of ZnO nanowires mimics that of the Au NPs at their tips. A quantitative study of the nanostructure size distribution after sequential annealing and growth steps evidences the occurrence of three nanoscale processes: (i) Ostwald ripening and/or coalescence of Au NPs before nanowire nucleation, (ii) Au-catalysed VLS nucleation and axial growth of ZnO nanowires and (iii) radial growth of nanowires by a vapour–solid process. These processes originate the NP and nanowire size evolution during the experiments. The present findings are interpreted in terms of Zn vapour pressure changes during carbo-thermal evaporation. PACS 61.46.+w; 68.65.-k; 81.16.Dn     

单根Sb掺杂ZnO微米线非平衡电桥式气敏传感器的制作与性能

通过使用化学气相沉积法,成功制备出超长、大尺寸的Sb掺杂ZnO微米线.基于非平衡电桥原理,利用单根Sb掺杂ZnO微米线作为非平衡电桥的一个桥臂,制作出了可以在室温环境下工作的气敏传感器原型器件.结果表明:室温下测得该传感器对20,50,100和200 ppm(1 ppm=10^-6)不同浓度的丙酮及乙醇气体的响应-恢复曲线均呈现为矩形形状,在空气及被测气体中均有稳定的电流值,并随着探测气体浓度的增大,器件的响应值也在逐渐增加.此外,还发现器件对丙酮气体具有更好的选择性,当丙酮气体浓度为200 ppm时,该传感器的响应时间为0.2 s,恢复时间为0.3 s,响应度高达243%.通过与普通电导式气敏传感器对比发现,采用这种非平衡电桥结构传感器可以明显地提高响应度,使响应和恢复时间更快.此外,还研究了器件的气体探测机理.     

Solution-processed Au@rGO/GaN nanorods hybrid-structure for self-powered UV,visible photodetector and CO gas sensors

Although metal nanoparticles (NPs) have been widely reported, Au NPs functionalized reduced graphene oxide (rGO)/GaN nanorods (NRs) for multi-functional applications are rarely discussed. The rGO is a well known transparent electrode and has been considering an alternative electrode to ITO in the current optoelectronic community. In this work, Au NPs functionalized rGO (Au@rGO)/GaN NRs hybrid structure probed for photodetector and CO gas sensing applications. The hybrid structure was characterized by scanning electron microscopy, transmission electron microscope, current-voltage characteristics, photo conductivity, and gas sensor measurements. The Au@rGO/GaN NRs showed higher photoresponsivity (λ = 382 nm, 516 nm) compared to rGO/GaN NRs at room temperature. The rising and falling times of Au@rGO/GaN NRs are faster than that of rGO/GaN NRs. The hybrid structure Au@rGO/GaN NRs exhibited high CO gas response compared to rGO/GaN NRs at room temperature (∼38% to the 20 ppm). Au NPs played an important role in terms of electronic and chemical changes in the hybrid structure for improving both photodetectors the CO gas response. Such a multi-functional hybrid device is an interest of various room temperature applications.     

Resonance characteristics of localized plasmonic structures with periodic ZnO nano-patterns

Localized plasmonic structures with the periodic ZnO nano-patterns are demonstrated to increase the sensing characteristics of plasmonic sensor. The ZnO nano-patterns with 30 and 50 nm thicknesses are formed on the Au thin film of 50 nm, which have the periodic nano-patterns of 300 nm. Localized plasmonic structures are optimized using the three-dimensional finite-difference time-domain method as a function of incident angle for the width and thickness of the ZnO nano-structures. Localized plasmonic structures with the periodic ZnO nano-holes are fabricated using the double exposure technique by laser interference lithography. The measured resonance angles of 47.5° and 54° are obtained in the localized plasmonic structures with the periodic ZnO nano-patterns of 30 and 50 nm thicknesses, respectively.     

Aggregation and fractal formation of Au and TiO<Subscript>2</Subscript> nanostructures obtained by fs-pulsed laser deposition: experiment and simulation

In the synthesis of nanostructures by pulsed laser deposition (PLD), a crucial role is played by the environmental deposition pressure and the substrate temperature. Due to the high temperature of nanoparticles (NPs) at landing, other factors may determine the structure of the resulting aggregates. Here, Au and TiO₂ nanostructures are obtained by non-thermal fs-PLD in ambient conditions. On Si(100), only TiO₂ NPs form fractals with areas up to ~ 1 × 10⁶ nm², while on quartz Au NPs also form fractals with areas up to ~ 5 × 10³ nm², a much smaller size with respect to the TiO₂ case. The aggregation is described by a simple diffusive model, taking into account isotropic diffusion of the NPs, allowing quantitative simulations of the NPs and fractal area. The results highlight the key role of substrate thermal conductivity in determining the formation of fractals.

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