Enhanced ferroelectric, dielectric and optical behavior in Li-doped ZnO nanorods

Enhancement in the dielectric and ferroelectric properties has been observed in case of Li-doped ZnO nanorods (NR). Effect of Li-doping on ZnO structure and its optical properties has also been reported. In high resolution TEM studies, the length and diameter of as-synthesized Li-ZnO nanorods were found in the range of 100-150 nm and 20-70 nm, respectively. XRD studies, Li-doped ZnO NR exhibited wurzite structure in which lattice parameter becomes larger than the pure ZnO NR. In dielectric studies, higher dielectric constant and a ferroelectric phase transition at 72 °C were observed. In ferroelectric studies, high remnant polarization of 0.873 μC/cm² and low coercive field of 0.592 kV/cm were observed, which were better than their values in bulk Li-doped ZnO (0.044 μC/cm² and 2.0 kV/cm, respectively). In UV-Vis spectra, low absorption band edge at 352 nm was observed due to the size effect in the ZnO nanorods. In addition, PL spectra show a blue shift in both UV and visible region as a result of doping. These results are discussed in the light of the nanorods of confined geometry.     

三维形貌ZnO一维纳米结构的微波水热合成、机理及性能研究

以Zn(NO3)2·6H2O和NaOH为原料,采用微波水热法成功合成了具有三维形貌的单晶ZnO一维纳米结构。采用XRD、SEM及紫外-可见光谱分析等手段对ZnO纳米结构及性能进行了表征;探讨了ZnO复杂纳米结构的形成机理。结果表明:在不同工艺条件下可分别合成ZnO纳米棒、纳米线、纳米推进器、纳米蒲公英及纳米纺锤等结构;微波在合成复杂ZnO纳米结构中起非常重要的作用;纳米ZnO紫外-可见光谱吸收带边出现红移现象。该法没有引入任何金属催化剂、模板或者表面活性剂,从而避免了去除残余添加剂的后续复杂工序。另外,与传统水热法相比,该法可以显著减少反应时间和降低反应温度。     

Growth and optical properties of ZnO nanorods prepared through hydrothermal growth followed by chemical vapor deposition

We report on the synthesis of high-quality ZnO nanorods by combining hydrothermal growth (HG) and chemical vapor deposition (CVD) processes. Vertically aligned and closely packed ZnO nanorods were grown by HG on a sputtered ZnO seed layer on a SiO₂/Si (0 0 1) substrate. The top surface of the HG-prepared ZnO nanorods showed very flat surfaces compared with that of the sputtered ZnO seed layer. Therefore, the HG-prepared ZnO nanorods were used as a new alternative seed material for the CVD growth of the ZnO nanorods. Vertical ZnO nanorods were grown by CVD on both the new HG-prepared nanorod seed material and the sputtered ZnO seed layer. The CVD-prepared ZnO nanorods on new HG-prepared nanorod seed material showed better crystalline quality and superior optical properties than the CVD-prepared ZnO nanorods on sputtered seed layer. The former showed negligible deep-level emissions at room temperature photoluminescence measurements. The intensity ratio of near-band-edge emissions to deep-level emissions from the former was about 910, but that from the latter was about 151. This implies that the HG-prepared ZnO nanorods can be used as a promising new seed material for nanostructure synthesis.     

Large-scale syntheses of uniform ZnO nanorods and ethanol gas sensors application

Uniform ZnO nanorods with a gram scale were prepared by a low temperature and solution-based method. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL). The results showed that the sample had uniform rod-like morphology with a narrow size distribution and highly crystallinity. Room-temperature PL spectra of these nanorods show an exciton emission around 382 nm and a negligible deep level emission, indicating the nanorods have high quality. The gas-sensing properties of the materials have been investigated. The results indicate that the as-prepared nanorods show much better sensitivity and stability. The n-type semiconductor gas sensor exhibited high sensitivity and fast response to ethanol gas at a work temperature of 400 °C. ZnO nanorods are excellent potential candidates for highly sensitive gas sensors and ultraviolet laser.     

纤维锌矿ZnO纳米棒的合成及高选择性酒精传感器的研制

以无机盐做前驱体，采用有机溶液氧化-还原法合成了ZnO纳米棒，对终产物通过XRD、Raman spectrum、SEM和TEM进行结构检测表明，产物为纤维锌矿型结构，呈棒状，直径大约为50～80nm，长度大约为500nm；对材料的气敏性能测试表明，基于该材料制成的气体传感器对酒精有很好的响应和很好的选择性，且响应-恢复迅速。     

ZnO纳米棒的制备及光催化性能研究

采用水热法制备ZnO纳米棒。利用X射线粉末衍射(XRD)仪和透射电镜(TEM)对其结构和形貌分别进行表征,并通过紫外-可见分光光度计分析ZnO纳米棒光降解甲基紫来研究其光催化活性。结果表明,以氢氧化钠和醋酸锌为原料,聚丙烯酰胺为表面活性剂制备得到直径约26nm,长度达400nm的单晶纤锌矿结构的ZnO纳米棒。添加ZnO纳米棒光催化剂时的光降解率为70%,未加ZnO纳米棒的光降解率为30%,表明ZnO纳米棒具有很好的光催化活性。     

Improving color rendering index of Mn-doped ZnO nanorods on silicon-based substrate

Porous silicon pillar array(PSPA) samples which are ideal substantial materials with dominant electronic and luminescence properties were prepared by surface etching method. ZnO nanorods with or without Mn doping grown uniformly and aligned onto PSPA regardless of lattice matching show various photoluminescence(PL)properties. The doped Mn ions in ZnO nanorods were directly observed by X-ray photoelectron spectroscopy(XPS),and ZnO structures were detected by X-ray diffraction(XRD). As the doping concentration increases,XRD peaks of ZnO nanorods shift to low angle. The influences of doping Mn ions on luminescence properties of ZnO nanorods were investigated. Except for the ultraviolet(UV) PL band, the broad PL band is observed at visible region. The band could be divided into three separate bands(orange, green and red) by Lorentzian deconvolution. The intensity of orange PL band firstly increases then decreases, and then gets the maximum at the doping Mn-to-Zn molar ratio of 2.0:100.0 which is the most effective doping concentration. The green PL band is attributed to zinc vacancy of ZnO, the orange PL band to Mn ions recombination of itself, and the red PL band to oxygen vacancy of ZnO, respectively. As the Mn-doped ZnO nanorods could emit yellow green luminescence excited by UV radiation, and doped Mn ions could improve the color rendering index of the luminescence, the nanorods could be used as promising white-light emitters in the future.     

Oriented growth of ZnO nanostructures on Si and Al substrates

Aligned ZnO nanorod arrays and oriented ZnO nanoplates were synthesized on Si and Al substrates, respectively, using a hydrothermal method without any surfactant. The process involved the deposition of ZnO seeds on the substrate and the oriented growth of ZnO nanostructure in aqueous solution. The ZnO seeds were indispensable for the alignment of ZnO nanorods and TEM and XRD analysis confirmed that the ZnO rods are single crystalline grown along [001] direction. Al substrate caused formation of (001) surface dominated ZnO nanoplates, in which ZnO preferential growth direction was suppressed. The photoluminescence spectra of the as-grown ZnO products were measured to indicate their structural and optical quality. These oriented ZnO nanostructures are expected to be prospectively applied in nanodevices fabrication.     

Growth of ZnO nanorod arrays on soft substrates by hydrothermal process

ZnO nanorod arrays with quite homogeneous size and shape were fabricated by introducing ZnO seed-layer as nucleation centers on the soft ITO substrates prior to the hydrothermal reaction. The samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and photoluminescence method. After the ZnO seed-layer is introduced, the resulting deposits on the substrates develop into nanorods, and the diameter decreases obviously to about 100 nm. Influences of the coated nanocrystal seed nuclei on the morphology of ZnO nanorod arrays were discussed. The results show that each nanorod is monocrystalline with wurtzite-type structure and oriented in c-axis direction. The increase of the intensity ratio of ultraviolet to visible emissions in room-temperature photoluminescence spectra and the decrease of the ultraviolet PL linewidths show the improvement of the quality of ZnO nanorods. A simple and effective method to synthesize ZnO nanorod arrays with fairly uniform size and shape on soft substrates is dip-coating ZnO nanocrystals prior to hydrothermal reaction, and it may be also feasible for the fabrication of other small-size metal oxide nanostructures on soft substrates.     

水溶性聚合物对液相法合成纳米氧化锌的影响

以[Zn(OH)_4]~(2-)为前驱体溶液,利用聚合物和表面活性剂的共同作用来控制纳米晶的生长,化学液相法合成了纳米ZnO 单晶.借助于X-射线衍射仪、透射电镜、紫外可见光谱分析仪等手段表征和探讨了氧化锌纳米晶的物相组成、显微结构和谱学特征.并讨论了反应时间、反应温度、反应物配比等因素对产物形态的影响以及水溶性聚合物和表面活性剂的添加对无机粒子的成核和晶体生长的影响.结果表明,所得产物物相为球形结构的颗粒状纳米氧化锌,直径约为50 nm,粒径分布均匀,样品在200～300 nm可见光区域内有强的紫外吸收峰.     

退火处理对氧化锌纳米棒形貌及气敏性能的影响（英文）

研究水热合成氧化锌纳米棒的高温热稳定性。采用X射线衍射和扫描电镜对氧化锌纳米棒的结构与形貌进行表征。采用热重分析研究氧化锌纳米棒在热处理过程中的失重情况。结果表明:在退火温度低于400°C时,氧化锌纳米棒具有较好的热稳定性。当退火温度超过600°C时,氧化锌纳米棒的长径比明显降低并且纳米棒的团聚趋势加剧。退火处理对氧化锌纳米棒的气敏性能具有显著影响。与未经退火处理的氧化锌纳米棒相比,经历400°C退火处理的氧化锌纳米棒对浓度为25×10-6的H2灵敏度可以从2.22提高至3.56。经历400°C热退火处理的氧化锌纳米棒对H2表现出最优的气敏性能。     

Comparative study of ZnO nanostructures grown on silicon (1 0 0) and oxidized porous silicon substrates with and without Au catalyst by chemical vapor transport and condensation

ZnO tetrapods and rods were grown on silicon and thermally oxidized porous silicon substrates with and without Au catalyst layer by carbothermal reduction of ZnO powder through chemical vapor transport and condensation method (CVTC). Porous silicon was fabricated by electrochemical etching of silicon in HF solution. The effect of substrates on morphology, structure and photoluminescence spectra of ZnO nanostructures has been studied. The texture coefficient (TC) of each sample was calculated from XRD data that demonstrated random orientation of ZnO nanostructures on the oxidized porous silicon substrate. Moreover, TC indicates the effect of Au catalyst layer on formation of more highly oriented ZnO nanorods. The morphology of the samples was investigated by SEM which confirms formation of ZnO nanostructures on oxidized porous silicon substrates with and without catalyst. A blue-green emission has been observed in ZnO nanostructures grown on Si and the oxidized PS substrates without Au catalyst layer by PL measurements.     

Synthesis of GaN nanorods on Si substrates with assistance of the volatilization of ZnO middle layers

GaN nanorods have successfully been synthesized on Si(111) substrates via ammoniating ZnO/Ga2O3 films at 950℃. Ga2O3 thin films and ZnO middle layers were deposited in turn on Si(111) substrates by r.f. magnetron sputtering system. ZnO volatilized at 950℃ in the ammonia ambience and Ga2O3 reacted to NH3 to fabricate GaN nanorods in the later ammoniating process. The volatilization of ZnO layers played an important role in the fabrication. The structure and composition of the GaN nanorods were studied by X-ray diffraction (XRD) and Fourier transform infrared spectrophotometer (FTIR). The orphology ofGaN nanorods was investigated using scanning electron microscopy (SEM) and transmission electronic microscope (TEM). The analyses of measured results revealed that GaN nanorods with hexagonal wurtzite stxucture were prepared by this method.     

热处理对TiO2溅射薄膜结构和光谱性能的影响

用直流反应磁控溅射法制备了TiO2薄膜,并对热处理前后试样的紫外可见光谱（UV-Vis spectrum）和荧光发射光谱（PL Spectrunm）做了研究。发现热处理后试样的紫外可见光谱在496nm处出现了一个较为明显的吸收峰，荧光发射光谱496．5nm处出现一个荧光发射带肩。X射线光电予能谱（XPS）的分析结果表明，热处理可使薄膜中晶格氧扩散出去，生成Ti^3＋离子和氧空位。结合XPS的分析结果和理论计算，可推断热处理后出现的位于496nm处的吸收峰和496．5nm处的荧光带肩可被指认为薄膜中Ti^3＋离子的d电子跃迁产生。     

热处理对TiO_2溅射薄膜结构和光谱性能的影响

用直流反应磁控溅射法制备了TiO2薄膜,并对热处理前后试样的紫外可见光谱(UV-Visspectrum)和荧光发射光谱(PLSpectrunm)做了研究。发现热处理后试样的紫外可见光谱在496nm处出现了一个较为明显的吸收峰,荧光发射光谱496.5nm处出现一个荧光发射带肩。X射线光电子能谱(XPS)的分析结果表明,热处理可使薄膜中晶格氧扩散出去,生成Ti3+离子和氧空位。结合XPS的分析结果和理论计算,可推断热处理后出现的位于496nm处的吸收峰和496.5nm处的荧光带肩可被指认为薄膜中Ti3+离子的d电子跃迁产生。     

Fabrication of Co-doped ZnO nanorods for spintronic devices

Herein, single-crystalline Zn_1?xCo_xO (0.0≤x≤0.10) nanorods were prepared using a facile microwave irradiation method. Structural analyses by X-ray diffraction and transmission electron microscopy revealed the incorporation of Co²⁺ in the lattice position of Zn²⁺ ions into the ZnO matrix. Field emission scanning electron microscopy and TEM micrographs revealed that the length and diameter of the undoped ZnO nanorods were about ～2 μm and ～200 nm, respectively. For Co-doped ZnO, the length and diameter were found to increase with an increase of Co doping. The selected area electron diffraction pattern indicated that the Zn_1?xCo_xO (0.0≤x≤0.10) nanorods had a single phase nature with the preferential growth direction along the [0 0 1] plane. Raman scattering spectra confirmed the shift of the E ₂ ^high mode toward a lower wave number, suggested successful doping of Co ions at Zn site into the ZnO. Magnetic studies showed that Co doped ZnO nanorods exhibited room temperature ferromagnetism and the magnetization value increased with an increase in Co doping. The synthesis method presented here is a simple approach to prepare ZnO based diluted magnetic semiconductors nanostructures for practical application to spintronic devices.     

Preparation of nitrogen-doped titania and its photocatalytic activity

Yellowish nitrogen-doped titania was produced through sol-gel method in mild condition, with the elemental ni- trogen derived from aqua ammonia. The titania catalysts were characterized using XRD, BET, TEM, XPS, and UV-Vis diffuse reflectance spectrophotometer, and their photocatalytic activities were evaluated under UV and visible light, respec- tively. The XRD results showed that all titania catalysts were anatase. More significantly, the crystallite size of nitro- gen-doped titania increased with an increase in N/Ti proportion, and the doping of nitrogen could extend the absorption shoulder into the visible-light region, thus it possessed a higher visible-light activity illustrated by decolorization of methyl orange (65.3%) under the irradiation of visible light, whereas pure titania showed little of such kind of visible light activity. The UV-light activity of nitrogen-doped titania catalysts was worse than that of pure titania and Degussa P25. In the range of N/Ti proportion of 4-10 mol%, the activity of nitrogen-doped titania weakened appreciably in the visible-light region as the N/Ti proportion increased, whereas a reverse relationship existed under the irradiation of UV light.     

ZnO and TiO2 1D nanostructures for photocatalytic applications

ZnO and TiO₂ 1D nanostructures (nanorods and nanotubes) were prepared by low-cost, low-temperature, solution-based methods and their properties and photocatalytic performance were studied. ZnO nanorod samples with titania and alumina shells were also prepared by solution-based methods, and their properties and photocatalytic performance were compared to that of bare ZnO nanorods. We found that ZnO and TiO₂ exhibited comparable photocatalytic performance. Faster dye degradation under simulated solar illumination was observed for ZnO, while under UV illumination faster degradation was observed for TiO₂. ZnO nanorods with titania shells exhibited inferior photocatalytic performance, while for alumina shells the performance was similar to bare ZnO. Reasons for observed differences are discussed, and the effect of the shell on photocatalytic activity is attributed to the changes in native defects at the ZnO surface/shell interface.     

基于氧化钛纳米管模板电沉积氧化锌纳米棒

研究了氧化锌纳米棒在用二次阳极氧化法制备的二氧化钛纳米管模板表面的电沉积生长。与一次阳极氧化法对比,以二次阳极氧化法获得的氧化钛纳米管薄膜为模板,更有利于形貌均一、取向一致的ZnO纳米棒的电沉积生长,并且在电解质溶液中添加六次甲基四胺(HMT)、适当延长沉积时间均可提高ZnO纳米棒的结晶度和择优生长趋势。当沉积电压为1.0~1.5 V时,可获得形貌规则的ZnO纳米棒;而电压继续增大时,ZnO沿c轴择优生长趋势消失,电沉积产物氧化锌纳米棒由六边形氧化锌纳米片取代。     

ZnO nanocoral reef grown on porous silicon substrates without catalyst

Porous silicon (PS) technology is utilized to grow coral reef-like ZnO nanostructures on the surface of Si substrates with rough morphology. Flower-like aligned ZnO nanorods are also fabricated directly onto the silicon substrates through zinc powder evaporation using a simple thermal evaporation method without a catalyst for comparison. The characteristics of these nanostructures are investigated using field-emission scanning electron microscopy, grazing-angle X-ray diffraction (XRD), and photoluminescence (PL) measurements of structures grown on both Si and porous Si substrates. The texture coefficient obtained from the XRD spectra indicates that the coral reef-like nanostructures are highly oriented on the porous silicon substrate with decreasing nanorods length and diameter from 800-900 nm to 3.5-5.5 μm and from 217-229 nm to 0.6-0.7 μm, respectively. The PL spectra show that for ZnO nanocoral reefs the UV emission shifts slightly towards lower frequency and the intensity increase with the improvement of ZnO crystallization. This non-catalyst growth technique on the rough surface of substrates may have potential applications in the fabrication of nanoelectronic and nanooptical devices.