微流控技术制备ZnO纳米棒及生物荧光检测性能研究

本研究设计并制备了一种微流控芯片并在其中水热合成了氧化锌(ZnO)纳米棒。利用扫描电子显微镜(SEM)和X射线衍射(XRD)研究了合成条件对ZnO纳米棒的形貌和晶体结构的影响。结果表明, 在微流控芯片中可制备得到致密的ZnO纳米棒, 其直径和长度随加热方式和制备时间的变化而改变。对比研究不同加热方式制备的ZnO纳米棒阵列检测异硫氰酸荧光素标记的羊抗牛IgG的性能, 发现局部加热方式制备的ZnO纳米棒检测荧光素标记蛋白的性能更佳, 在10 pg/mL~1 μg/mL范围内线性良好, 相关系数为0.99209。在此基础上, 用局部加热制备的ZnO纳米棒检测人甲胎蛋白(AFP), 其最低检测限可达1 pg/mL。这些结果表明, 微通道中合成的ZnO纳米棒适用于多通道荧光检测。     

Optical and magnetic properties of copper doped ZnO nanorods prepared by hydrothermal method

Surfactant free ZnO and Cu doped ZnO nanorods were synthesized by hydrothermal method. The formation of ZnO:Cu nanorods were confirmed by scanning electron microscopy, X-ray diffraction and Raman analysis. Diffuse reflectance spectroscopy results shows that band gap of ZnO nanorods shifts to red with increase of Cu content. The orange-red photoluminescent emission from ZnO nanorods originates from the oxygen vacancy or ZnO interstitial related defects. ZnO:Cu nanorods showed strong ferromagnetic behavior, however at higher doping percentage of Cu the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced. The presence of non-polar E ₂ ^high and E ₂ ^low Raman modes in nanorods indicates that Cu doping didn’t change the wurtzite structure of ZnO.     

White-light-controlled resistive switching and photovoltaic effects in TiO2/ZnO composite nanorods array at room temperature

White-light-controlled resistance switching and photovoltaic effects in TiO₂/ZnO composite nanorods array grown on fluorine-doped tin oxide (FTO) substrate by hydrothermal process were investigated. The average length of TiO₂/ZnO nanorods is about 3 μm, and the average diameter is about 200 nm. ZnO nanoparticles with size 5–10 nm are embedded in TiO₂ base material. The current–voltage characteristics of Ag/[TiO₂/ZnO]/FTO device demonstrate an outstanding rectifying property and bipolar resistive switching behavior. Specially, the resistive switching behavior can be regulated by white-light illuminating. In addition, this structure also exhibits a substantial white-light photovoltaic effect. This study is helpful for exploring the multifunctional materials and their applications in nonvolatile multistate memory devices and solar cells.     

Continuous production of fine zinc oxide nanorods by hydrothermal synthesis in supercritical water

Continuous production of highly crystalline ZnO nanorods by supercritical hydrothermal synthesis was reported in this article. Zinc nitrate aqueous solution was pressurized to 30 MPa at room temperature and rapidly heated to 673 K by mixing with supercritical water and then fed into a tubular reactor. Residence time is about 10 s. Production of ZnO nanorod particles with uniform particle size distribution showed a strong ultraviolet light emission at room temperature. This article also reported in-situ surface modification of ZnO nanorods with organic reagents by the supercritical hydrothermal synthesis.     

Effect of leavening agent on structural and photocatalytic properties of ZnO nanorods

In the present work, we have demonstrated a simple, facile, one-step, rapid and cost effective synthesis of ZnO nanorods through the thermal decomposition of zinc acetate and leavening agent (NaHCO₃). The silver nanoparticles (AgNPs) were deposited on the surface of ZnO nanorods by photocatalytic reduction of Ag (I) to Ag(0). As synthesized ZnO nanorods and Ag–ZnO nanocomposites were characterized by using X-ray Diffraction, field emission scanning electron microscope, high-resolution transmission electron microscope and diffuse reflectance spectroscopy. The photocatalytic activities of the ZnO nanorods and Ag–ZnO nanocomposites were evaluated for the photodegradation of Methyl Orange (MO) under UV and sunlight irradiation. The use of common leavening agent helps to prevent the aggregation of ZnO nanorods, further it hinders crystallite growth and narrowing the diameter of nanorods by the evolution of carbon dioxide during calcination. The ZnO nanorods and Ag–ZnO nanocomposite exhibited an enhanced photocatalytic activity and separation of photogenerated electron and hole pairs. Due to effect of leavening agent and AgNPs deposited on surface of ZnO nanorods finds best catalyst for the 99% degradation of MO within 30 min compared to ZnO.     

Synthesis of violet light emitting single crystalline ZnO nanorods by using CTAB-assisted hydrothermal method

ZnO nanorods were grown by cetyl trimethylammonium bromide assisted hydrothermal technique from a single molecular precursor. The phase and structural analysis were carried out by X-ray diffraction technique and Raman spectroscopy, respectively. The phase and structural analysis has suggested that as prepared nanorods have hexagonal wurzite structure. Morphology of the nanorods was investigated by electron microscopy techniques which showed the formation of well dispersed nanorods of 100 ± 10 nm in diameter and 900 ± 100 nm in length. Optical properties were investigated by photoluminescence spectroscopy. As prepared ZnO nanorods have shown intense room temperature photoluminescence peak in the violet region at 403 nm. Absence of defect mediated green luminescence peak suggests the formation of well crystalline ZnO nanorods without any impurities or structural defects.     

Growth and optical properties of ZnO nanorods by introducing ZnO sols prior to hydrothermal process

ZnO nanorods of 25 nm with quite homogeneous size and shape have been fabricated by introducing ZnO sols as nucleation centers prior to the hydrothermal reaction. The samples were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, photoluminescence and resonant Raman spectra. After ZnO sols are introduced, the width of the resulting nanorods decreases above an order of magnitude and the aspect ratio increases 5 times. The increase of the intensity ratio of ultraviolet to visible emissions in room-temperature photoluminescence spectrum and the decrease of the Raman linewidths show the improvement in the quality of ZnO nanorods. Influences of the number of seed nuclei and the aging time of ZnO sols on the morphology of ZnO nanorods are discussed.     

Sonochemical synthesis of nitrogen doped ZnO nanorods: effect of anions on growth and optical properties

Sonochemical synthesis of nitrogen doped zinc oxide (ZnO:N) nanorods using acetate and nitrate of the starting materials is reported. X-ray diffraction studies reveal the formation of hexagonal wurtzite phase of ZnO in both the cases whereas the crystallite size is found to be greater in acetate route. Precursor dependent growth process is observed as the time period for precipitation is found to be different with different starting materials. Electron microscopic studies show the formation of rod like structures of ZnO and ZnO:N in both acetate and nitrate routes. But, high aspect ratio and uniformity in the morphology of ZnO:N nanorods is observed in acetate route. High resolution images and selected area diffraction patterns of ZnO:N illustrate the nanorods to be c-axis oriented in both the cases. But in nitrate medium, the growth along [0001] direction is affected due to the adsorption of NO₃ ^? ions onto polar Zn²⁺ surface leading to smaller length of the nanorods. FTIR studies also support these results showing the existence of sharp N–O symmetric stretching in ZnO:N in nitrate route. Photoluminescence (PL) measurements show red shift of excitonic emission band for ZnO in acetate route.     

A simple and novel low-temperature hydrothermal synthesis of ZnO nanorods

A new simple low-temperature hydrothermal process without addition of any surfactant or complexing agent was put forward to synthesize uniform ZnO nanorods, in which hydrazine hydrate instead of NaOH was used as mineralizer. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and UV-vis diffuse reflectance spectroscopy were used to characterize the product, the results of which reveal that uniform ZnO nanorods approximately 70 nm in width and 2 μm in length were formed at 150°C within 8 h. Prior to the hydrothermal process hydrazine hydrate reacted with ZnCl₂ solution to form a complex, and the complex slowly decomposed in the hydrothermal process. All these characteristics were favorable to this additive-free hydrothermal synthesis of ZnO nanorods. The text was submitted by the authors in English.     

Performance of polymer/ZnO hybrid photovoltaic devices determined by reaction time for oriented ZnO nanorod growth

The performance of hybrid polymer/metal oxide photovoltaic devices based on poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) and oriented ZnO nanorods is studied. The ZnO nanorods on indium tin oxide-coated glass were prepared by hydrothermal method, where the length and the defect concentration of ZnO nanorods were controlled by the reaction time (T_r) for nanorod growth. Increasing T_r results in longer ZnO nanorods and higher defect concentration. Results show that both photocurrent and electron lifetime have strong dependence on the nanorod length (i.e., growth time) due to the exponential attenuation of incident light intensity in the device, offering a peak conversion efficiency of 0.337% under 1.5 AM illumination for T_r = 120 min. Combinational analyses of the data in this experiment and the previous data for the electrodeposited ZnO nanorods provide the insights into the dependence of the device performance on the intrinsic property of the ZnO nanorods.     

The effect of seed layer thickness on alignment and morphology of ZnO nanorods

Thin films of ZnO of 20, 40,160 and 320 nm thickness were deposited on Si (100) substrates by rf-magnetron sputtering and then nanorods were grown on the seed layer at 95 °C for 2 h. The ZnO nanorods were synthesized in C₆H₁₂N₄ and Zn (NO₃)₂·6H₂O solution by a hydrothermal method and the effect of seed layer thickness on the alignment, diameter, density and growth rate of nanorods was studied.The results revealed that the alignment of nanorods depended on crystallinity, grain size and roughness frequency of the sputtered seed layer, so that, with increase of seed layer thickness, crystallinity improved. In addition the grain size increased and the roughness frequency decreased and hence alignment and diameter of nanorods increased.Finally, we present a model for the effect of seed layer thickness on the alignment and diameter of the nanorods.     

The effect of seed layer thickness on alignment and morphology of ZnO nanorods

Thin films of ZnO of 20, 40,160 and 320 nm thickness were deposited on Si (100) substrates by rf-magnetron sputtering and then nanorods were grown on the seed layer at 95 °C for 2 h. The ZnO nanorods were synthesized in C₆H₁₂N₄ and Zn (NO₃)₂·6H₂O solution by a hydrothermal method and the effect of seed layer thickness on the alignment, diameter, density and growth rate of nanorods was studied.The results revealed that the alignment of nanorods depended on crystallinity, grain size and roughness frequency of the sputtered seed layer, so that, with increase of seed layer thickness, crystallinity improved. In addition the grain size increased and the roughness frequency decreased and hence alignment and diameter of nanorods increased.Finally, we present a model for the effect of seed layer thickness on the alignment and diameter of the nanorods.     

CTAB-assisted hydrothermal synthesis of single-crystalline copper-doped ZnO nanorods and investigation of their photoluminescence properties

A simple CTAB-assisted hydrothermal synthesis of undoped and copper-doped ZnO nanorods is reported. The phase and structural analysis carried out by X-ray diffraction, shows the formation of hexagonal wurtzite structure of ZnO. Morphology of the ZnO nanorods was investigated by electron microscopy techniques which showed the formation of well dispersed regular shape ZnO nanorods of 100 ± 10 nm in diameter and 900 ± 100 nm in length. However, size of the copper doped ZnO nanorod slightly increased with increasing copper concentration. Furthermore, the selected area electron diffraction pattern and high resolution transmission electron microscopy reveal that both the undoped and copper doped ZnO nanorods were single crystalline in nature and preferentially grew up along [0001] direction. Optical property was investigated by photoluminescence spectroscopy. The effects of copper doping on the photoluminescence property of ZnO nanorods were investigated.     

Effect of reaction conditions on the morphology and optical properties of ZnO nanocrystals

We report a simple hydrothermal method at low temperature for synthesis of zinc oxide (ZnO) nanorods followed by ultrasonication. The samples were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), UV–Vis absorption spectrophotometer and photoluminescence (PL) spectroscopy. The XRD results shows the prepared ZnO nanocrystals are in wurtzite structure. TEM results indicate the growth of ZnO nanorods with increasing reaction stirring time and morphology also get affected after ultrasonication. PL studies also reveal the presence of defects considered as the main reason for the green emission in PL with increasing reaction time and blue shift in UV emission corresponds to reduction of tensile strain.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

Selective growth of ZnO nanorods for gas sensors using ink-jet printing and hydrothermal processes

Selective growth of ZnO nanorod arrays with well-defined areas was developed to fabricate the NO₂ gas sensor. The seed solution was ink-jet printed on the interdigitated electrodes. Then, vertically aligned ZnO nanorods were grown on the patterned seed layer by the hydrothermal approach. The influences of seed-solution properties and the ink-jet printing parameters on the printing performance and the morphology of the nanorods were studied. Round micropattern (diameter: 650 μm) of ZnO nanorod arrays is demonstrated. The dimensions and positions of the nanorod arrays can be controlled by changing the printed seed pattern. The effects of nanorod structure and nanorod size on the gas-sensing capability of ZnO nanorod gas sensors were demonstrated. Due to the high surface-to-volume ratios of the nanorod-array structure, the ZnO nanorod gas sensor can respond to 750 ppb NO₂ at 100 °C. The sensors without baking treatment exhibit the typical response of a p-type semiconductor. However, only the response of n-type semiconductor oxides was observed after the annealing treatment at 150 °C for 2 h.     

海胆形氧化锌纳米结构的制备与光催化性能

以Zn(AC)2.2H2O为原料,NH3.H2O为络合剂,在NaBH4辅助下140℃水热反应2 h制备出ZnO纳米棒自组装的海胆形结构。采用X射线衍射仪、扫描电镜和透射电镜对产物进行表征。结果表明,海胆形ZnO结构的直径约为3～17μm,它是由直径约为100 nm,长度约为500 nm～3μm范围的ZnO纳米棒自组装而成。提出了ZnO纳米棒自组装海胆形结构的可能生长机理。NaBH4与溶液中的少量H+结合生成H2气泡,ZnO纳米晶吸附在H2的气液界面形成了纳米颗粒自组装的微球,随着反应时间的延长,组装成微球的ZnO纳米颗粒沿[0001]方向取向生长成ZnO纳米棒,最终形成ZnO纳米棒自组装的海胆形颗粒。室温下以海胆形ZnO纳米结构和ZnO纳米棒为光催化剂,以偶氮染料甲基橙作为光催化研究对象,紫外光照70 min,对甲基橙的降解率分别为97%和67%。     

Structural and optical properties of hydrothermally grown zinc oxide nanorods on polyethersulfone substrates as a function of the growth temperature and duration

Zinc oxide (ZnO) nanorods were grown on polyethersulfone substrates with a seed layer by hydrothermal synthesis. The effects of the growth temperature and duration on the structural and optical properties of the ZnO nanorods were investigated by X-ray diffraction, field emission scanning electron microscope and photoluminescence measurements. Improvement of the structural properties was confirmed when the ZnO nanorods were grown at a moderate thermal energy. Thermal energies that were too high or too low resulted in structural degradation: low thermal energies did not provide enough energy for the ZnO growth, and high thermal energies contributed to improper growth by creating an uncommon flake-like structure. Photoluminescence measurements showed that the near-band-edge emission to deep-level emission peak ratio increases with increasing growth temperature at growth duration of 5 h.     

Synthesis of well dispersed, regular shape ZnO nanorods: effect of pH, time and temperature

In this paper we presented a systematic study on the morphological variation of ZnO nanostructure by varying the pH of precursor solution, reaction time and reaction temperature via cetyl trimethylammonium bromide-assisted hydrothermal method. The phase and structural analysis was carried out by X-ray diffraction, showed the formation of single phase ZnO with hexagonal wurtzite structure in all the specimens. Morphological and structural analysis was carried out by scanning electron microscopy and transmission electron microscopy showed that the shape of ZnO nanorods were greatly influenced by pH of precursor precipitate while size was affected by reaction time as well as temperature. The selected area diffraction pattern showed that the as synthesized ZnO nanorods were single crystalline in nature and preferentially grow along [0001] direction. A plausible growth mechanism of as prepared ZnO nanostructures was discussed in detail. Furthermore, the optical property of as prepared ZnO nanostructures was studied by photoluminescence spectroscopy.     

Structural and morphological studies of zinc oxide incorporating single-walled carbon nanotubes as a nanocomposite thin film

Pure zinc-oxide and a composition of zinc oxide-single walled carbon nanotubes (ZnO-SWCNTs) thin films were prepared by using a sol–gel doctor blade technique. A precursor of zinc acetate dehydrate (Zn(CH₃COO)₂·2H₂O), absolute ethanol (C₂H₅OH) and triethanolamine were mixed in one solution. Non-acid treatment SWCNTs were doped in the prepared solution. Structural and morphological properties of ZnO and ZnO-SWCNTs thin films were studied by means of X-ray diffractometer (XRD), field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM). XRD measurements indicated that the crystallite size of ZnO was bigger than the crystallite size of ZnO-SWCNTs; 0.4331 and 0.3386 nm, respectively. The FESEM images showed the hexagonal and nanorod structures of ZnO thin film and a broccoli-like ZnO nanostructures coated with CNTs for ZnO-SWCNTs thin film. The AFM analysis revealed smoother surface morphology of ZnO-SWCNTs thin film compared to the surface of pure ZnO thin film. TEM results captured the inner structures of ZnO and ZnO-SWCNTs. Inner and outer diameter of non-acid treatment SWCNTs were recorded about 5.09 and 14.95 nm, respectively. Photovoltaic performance of ZnO-SWCNTs based dye-sensitized solar cell (DSSC) showed high power conversion efficiency of 0.102 % compared to ZnO based DSSC (0.019 %). This study suggests that SWCNTs should be acid-treated to produce highly porous structure and greater surface area for better photovoltaic performance of the DSSCs.