Nonresonant optical nonlinearity of ZnO composite nanoparticles with different interfacial chemical environments

 ZnO nanoparticles coated by surfactant molecules were synthesized by microemulsion method. Under proper thermal treatment, a new ZnO/surfactant composite nanoparticles were formed and exhibited an unique optical property. The third-order optical nonlinearity χ⁽³⁾ of ZnO composite nanoparticles with different interfacial chemical environment were measured by single-beam Z-scan technique, the sign and magnitude of both the real and imaginary parts of χ⁽³⁾ at 790 nm were measured to be: –5.2×10^–16 m²/W and 11.6 cm/Gw for ZnO/DBS composite nanoparticles (DBS, dodecyl benzene sulfonate, anionic surfactant); and –2.2x10^–17 m²/W, 0.45 cm/Gw for ZnO/CTAB composite nanoparticles (CTAB, cetyltrimethyl ammonium bromide, cationic surfactant). The ultrafast nonlinear response time (∼250 fs) measured by time-resolved pump-probe technique at excitation wavelength of 647 nm suggests that the optical nonlinearity below band-gap originate mainly from a rapid electronic polarization process or virtual process such as the optical Stark effect. Received: 19 December 1997 / Accepted: 22 December 1997     

Rapid growth of nanotubes and nanorods of würtzite ZnO through microwave-irradiation of a metalorganic complex of zinc and a surfactant in solution

Large quantities of single-crystalline ZnO nanorods and nanotubes have been prepared by the microwave irradiation of a metalorganic complex of zinc, in the presence of a surfactant. The method is simple, fast, and inexpensive (as it uses a domestic microwave oven), and yields pure nanostructures of the hexagonal würtzite phase of ZnO in min, and requires no conventional templating. The ZnO nanotubes formed have a hollow core with inner diameter varying from 140–160 nm and a wall of thickness, 40–50 nm. The length of nanorods and nanotubes varies in the narrow range of 500–600 nm. These nanostructures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The ZnO nanorods and nanotubes are found by SAED to be single-crystalline. The growth process of ZnO nanorods and nanotubes has been investigated by varying the surfactant concentration and microwave irradiation time. Based on the various results obtained, a tentative and plausible mechanism for the formation of ZnO nanostructures is proposed.     

Investigation of the characteristics of a colloidal solution and its solid phase obtained through ablation of zinc in water by high-power radiation from a copper vapor laser

Experimental data are presented on the study of a colloidal solution created through zinc ablation in water by means of high-power radiation from a copper vapor laser. Absorption spectrum analysis is performed in the optical range of λ = 200–600 nm. The structural composition and morphology of the solid phase isolated from the colloid are determined by means of X-ray diffractometry, and atomic-force and scanning electron microscopy. It is demonstrated that ZnO, as well as zinc, nanoparticles, which oxidize to ZnO under colloid ageing, are present in the colloid composition after target irradiation. The ZnO end product has a complex structure, which is based on hexagonal crystals 40 × 80 nm in size on average.     

Photocatalytic activity of TiO2-capped ZnO nanoparticles

Using a combined hydrothermal and sol–gel route, TiO₂ -capped ZnO nanoparticles with an average size of 60 nm were prepared. The titania shell was amorphous with a thickness of ~10 nm. Formation of Zn₂TiO₄ phase at higher calcination temperature was noticed. Effects of Ti/Zn molar ratio and coating time on the thickness of TiO₂ shell and the photoactivity of the particles for decolorization of Methylene Blue (MB) under UV lamp irradiation (3 mW/cm²) were investigated. The nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, fourier-transform infrared spectrometry (FTIR), diffuse reflectance spectroscopy (DLS), and atomic absorption spectroscopy. Analysis of the photoactivity results according to Langmuir–Hinshelwood model revealed a two-step decolorization process with a high kinetics rate at the early stage followed by a slower step. The capped nanoparticles synthesized under specific conditions exhibited higher photodecolorization yield and faster kinetics in comparison to the uncoated ZnO and P25-Degussa TiO₂ nanoparticles.     

Growth of compact arrays of optical quality single crystalline ZnO nanorods by low temperature method

We report the synthesis and optical properties of compact and aligned ZnO nanorod arrays (dia, ∼ 50–200 nm) grown on a glass substrate with varying seed particle density. The suspension of ZnO nanoparticles (size, ∼ 15 nm) of various concentrations are used as seed layer for the growth of nanorod arrays via selfassembly of ZnO from solution. We studied the effect of various growth parameters (such as seeding density, microstructure of the seed layer) as well as the growth time on the growth and alignment of the nanorods. We find that the growth, areal density and alignment of the nanorods depend on the density of seed particles which can be controlled. It is observed that there is a critical density of the seed particles at which nanorod arrays show maximum preferred orientation along [002] direction. The minimum and maximum radius of the aligned nanorods synthesized by this method lie in the range 50–220 nm which depend on the seeding density and time of growth. These nanorods have a bandgap of 3.3 eV as in the case of bulk crystals and show emission in the UV region of the spectrum (∼ 400 nm) due to excitonic recombination and defect related emission in the visible region.     

Optical and electrical properties of aluminum-doped zinc oxide nanoparticles

Aluminum-doped zinc oxide nanopowders were prepared using a surfactant assisted complex sol–gel method, and were characterized using inductively coupled plasma, X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and UV–Vis spectroscopy. Al was effectively doped into the ZnO matrix with concentrations up to 6.00 atomic ratio percents (at.%). X-ray diffraction results revealed that all of the nanoparticles had a pure hexagonal wurtzite structure free of any impurities when annealing temperature was below 1273 K. The optical band gap of the nanopowders, which was affected by the Al-doping concentration, reached a maximum of 3.43 eV when ZnO was doped with 4.00 at.% Al. The effect of post-annealing temperature and vacuum conditions on the resistivities of the Al-doped ZnO nanoparticles was also investigated. And the lowest volume resistivity (1.2 Ω cm) was achieved by annealing the Al-doped ZnO nanoparticles in a vacuum at 1173 K for 2 h.     

Synthesis,structure, and room-temperature ferromagnetism of Ni-doped ZnO nanoparticles

In this paper, Ni-doped ZnO (Zn_1−x Ni _x O, in which 0 ≤ x ≤ 0.05) diluted magnetic semiconductors nanoparticles are prepared by an ultrasonic assisted sol–gel process. Transmission electron microscopy shows sphere-like nanoparticles with an average size of about 25 nm. From the analysis of X-ray diffraction, the Ni-doped ZnO nanoparticles are identified to be a wurtzite structure, but impurity phases are observed when the Ni content x reaches 0.05. Sample structures are further studied by Raman spectra, from which a broad and strong Raman band in the range of 500–600 cm⁻¹ is observed in Zn_1−x Ni _x O. With the increment of x, wurtzite structures degrade gradually. The magnetic properties are measured using superconducting quantum interference device at room temperature; the Zn_1−x Ni _x O (x ≤ 0.02) nanoparticles show ferromagnetism. However, for the sample of Zn_0.95Ni_0.05O, paramagnetism is observed, which may be ascribed to ferromagnetic–antiferromagnetic competition.     

Sonochemical synthesis of silver nanoparticles in Y-zeolite substrate

Silver ions can be reduced by 24 kHz ultrasonic waves in ion-exchanged Ag⁺–Y zeolite. In this research, silver ions were introduced into the nano-porous (1.2 nm) zeolite lattice by ion-exchange route. After the reduction process, silver nanoparticles were placed in the cavities, with a size of about 1 nm and also on the external surfaces of the zeolite, with sizes about less than 10 nm. Fast and simple lab-scale reduction of silver ions in the zeolite is important for researchers who work on catalytic properties of metallic silver–zeolite. Several reduction methods have been reported but reduction by ultrasonic waves is a new, simple, and size-controllable method with a high practical value which does not need any complicated facilities. In a sonochemical process, a huge density of energy is provided by the collapse of bubbles which formed by ultrasonic waves. The released energy causes the formation of reducing radicals that consequently reduce the silver ions. It is concluded that the higher silver content may result in the formation of larger silver crystals on the external surface of zeolite crystals. Also, the addition of 1-propanol and 2-propanol to the aqueous reaction medium does not cause better reduction. In addition, increasing the irradiation time and ultrasonic power does not affect the silver crystal growth significantly but the extent of silver ion reduction increases when the power of ultrasonic waves increases. All samples were irradiated under the same ultrasonic conditions. The samples were analyzed by XRD, EDS, SEM, and TEM.     

ZnO nanoparticles supported on mesoporous MCM-41 and SBA-15: a comparative physicochemical and photocatalytic study

A simple solvothermal impregnation method was used to prepare ZnO nanoparticles supported on MCM-41 and SBA-15. X-ray powder diffraction, N₂ adsorption–desorption, Electron Probe Micro Analysis (EPMA), and UV–vis spectroscopy were used to characterize the prepared materials. The influence of the ZnO loading of different supports on the structural characteristics and the photocatalytic activity toward degradation of methylene blue in water under ultraviolet irradiation were investigated. Wide angle X-ray diffraction and UV–vis Diffuse Reflectance confirmed the existence of ZnO phase. A much smaller influence of impregnation with ethanolic zinc salt solution on the porosity was observed for SBA-15 compared with MCM-41. Finally, the adsorption and photocatalytic activity of the ZnO/mesoporous materials depend on porous characteristics of the support materials.     

Facile preparation of Ag/ZnO nanoparticles via photoreduction

Ag/ZnO nanoparticles can be obtained via photocatalytic reduction of silver nitrate at ZnO nanorods when a solution of AgNO₃ and nanorods ZnO suspended in ethyleneglycol is exposed to daylight. The mean size of the deposited sphere like Ag particles is about 5 nm. However, some of the particles can be as large as 20 nm. The ZnO nanorods were pre-prepared by basic precipitation from zinc acetate di-hydrate in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide. They are about 50–300 nm in length and 10–50 nm in width. Transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDS), X-ray powder diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) were used to characterize the resulting Ag/ZnO nanocomposites.     

Growth of aligned arrays of ZnO nanorods by low temperature solution method on Si surface

We report growth of ZnO nanorods by low temperature (<100°C) solution growth method. The substrates (Si, glass and fused Quartz) were seeded by pre-coating with ZnO nanoparticles (4–7 nm diameter) prepared by chemical precipitation route. Nanorods were grown on the seeded substrate in aqueous solution of Zinc Nitrate and Hexamethylenetetramine (HMT). The growth process lasts for up to 8 h and at the maximum time of growth, the nanorods have a width of ∼230–250 nm and length of ∼1.5–1.6 μm. The growth process after some initial growth (<2 h) preserves the aspect ratio and leads to about 90% texturing along the (002) direction. The growth of the nanorods was studied with time and observed growth data suggests a two-stage growth process. The nanorods have a well-defined hexagonal morphology and have a Wurtzite structure. The nanorods were characterized by different techniques and have a band gap of 3.25 eV.     

Quenching of photocatalytic activity and enhancement of photostability of ZnO particles by polydimethysiloxane coating

ZnO particles with a size range of 50–150 nm were coated with polydimethylsiloxane (PDMS) with a thin film thickness of 3–4 nm using a simple ambient-pressure chemical vapor deposition method. Surfaces consisting of the PDMS-coated ZnO nanoparticles were found to be superhydrophobic with a water contact angle >160°. The superhydrophobicity was sustained in the presence of UV light. Photocatalytic activity and photocorrosion of ZnO were nearly completely quenched in the presence of PDMS-coating. It is suggested that our PDMS-coating can be of potential interest for the application of ZnO in UV protection agents and energy and electronic devices.     

ZnO nanowire/TiO2 nanoparticle photoanodes prepared by the ultrasonic irradiation assisted dip-coating method

Hybrid ZnO/TiO₂ photoanodes for dye-sensitized solar cells were prepared by combining ZnO nanowire (NW) arrays and TiO₂ nanoparticles (NPs) with the assistance of the ultrasonic irradiation assisted dip-coating method. Results show that the ultrasonic irradiation was an efficient way to promote the gap filling of TiO₂ NPs in the interstices of ZnO NWs. Hybrid ZnO NW/TiO₂ NP electrodes prepared with ultrasonic treatment exhibited better gap filling efficiency and higher visible absorptance. The overall conversion efficiency of the hybrid electrode was 0.79%, representing 35% improvement compared with that of the traditional one (0.58%). The enlarged surface area and improved attachments of TiO₂ NPs onto the walls of ZnO NWs induced by the application of ultrasonic irradiation may be the underlying reason. Electrochemical impedance spectroscopy measurements indicated that hybrid electrodes combined the advantages of improved electron transport along the ZnO NWs and increased surface area provided by infiltrated TiO₂ NPs, both of which are responsible for the improved cell efficiency.     

Characterization of hot extruded Mg/SiC nanocomposites fabricated by casting

Mg–1%SiC nanocomposites were fabricated using an ultrasonic cavitation based casting method, resulting in the dispersion of the reinforcing SiC nanoparticles to form Mg–metal matrix nanocomposite (Mg–MMNC) billets. The MMNC billets were then processed using hot extrusion at 350 °C. Micrographic observations illustrate a significant grain size reduction and the presence of microbands that align the SiC nanoparticles parallel to the direction of extrusion for Mg–MMNCs. Observations from the cross-section at 90° of the extrusion direction show uniform nanoparticles dispersion. Results from the extruded Mg–MMNCs tensile testing at different temperatures (25, 125 and 177 °C) reveal an increase of the yield strength, ultimate tensile strength, and ductility values as compared to the un-reinforced and extruded Mg-alloy; such increase was also observed from the microhardness testing results where an increase from 19 to 34% was measured.     

Visible light-activated cadmium-doped ZnO nanostructured photocatalyst for the treatment of methylene blue dye

An attempt was made to prepare Cd-doped ZnO photocatalyst for visible light assisted degradation of a textile dye (methylene blue, MB) in aqueous solutions by a traditional sol–gel process. The as-prepared nanoparticles were characterized by X-ray diffraction, UV–vis diffuse reflectance spectroscopy, and photoluminescence spectra techniques. The results showed that the Cd-doped ZnO possess the single-phase hexagonal wurtzite structure. The photocatalytic activity of the nanoparticles under visible light was investigated by measuring the photodegradation of MB in aqueous dispersion. The effects of key operation parameters such as initial dye concentration, catalyst loading as well as initial pH value on the decolorization extents were investigated. The results indicate that the decolorization of the organic molecule followed a pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. Under the optimum operation conditions, approximately 85.0% dye removal was achieved within 3.5 h.     

Use of silane coupling agent for surface modification of zinc oxide as inorganic filler and preparation of poly(amide-imide)/zinc oxide nanocomposite containing phenylalanine moieties

A series of novel poly(amide?Cimide)/ZnO nanocomposites with modified ZnO nanoparticles contents was prepared by ultrasonic irradiation. For this purpose, surface of ZnO nanoparticle was modified with $\boldsymbol\gamma$ -aminopropyltriethoxysilane as a coupling agent. Then the effect of surface modification on dispersion of nanoparticles, thermal stability and UV absorption property of the obtained nanocomposites were investigated. The resulting novel nanocomposites were characterized by several techniques. Field emission scanning electron microscopy and transmission electron microscopy analyses of the nanocomposites were performed in order to study the dispersion of nanofillers in the polymer matrix. According to thermogravimetry analysis results, the addition of ZnO nanoparticles improved thermal stability of the obtained nanocomposites. Since the resulting nanocomposites contain phenylalanine amino acid and ZnO, they are expected to be biocompatible as well as biodegradable.     

Au/ZnO nanocomposites: Facile fabrication and enhanced photocatalytic activity for degradation of benzene

Au nanoparticles supported on highly uniform one-dimensional ZnO nanowires (Au/ZnO hybrids) have been successfully fabricated through a simple wet chemical method, which were first used for photodegradation of gas-phase benzene. Compared with bare ZnO nanowires, the as-prepared Au/ZnO hybrids were found to possess higher photocatalytic activity for degradation of benzene under UV and visible light (degradation efficiencies reach about 56.0% and 33.7% after 24 h under UV and visible light irradiation, respectively). Depending on excitation happening on ZnO semiconductor or on the surface plasmon band of Au, the efficiency and operating mechanism are different. Under UV light irradiation, Au nanoparticles serve as an electron buffer and ZnO nanowires act as the reactive sites for benzene degradation. When visible light is used as the light irradiation source, Au nanoparticles act as the light harvesters and photocatalytic sites alongside of charge-transfer process, simultaneously.     

Synthesis and optical characteristics of ZnO nanocrystals

Zinc oxide nanomaterials with an average particle size of 20–30 nm are readily synthesized by the reaction of zinc acetate and oxalic acid under hydrothermal conditions. The samples are characterized by XRD, SEM, TEM, UV and photoluminescence (PL) studies. The average crystal size of the as prepared ZnO nanopowder is determined by XRD and the values are in good agreement with the TEM analysis. UV absorption spectra revealed the absorption at wavelength < 370 nm indicating the smaller size of ZnO nanoparticles. The quality and purity of ZnO nanomaterial crystalline samples are confirmed by photoluminescence spectra.     

Mg–6Zn/1.5%SiC nanocomposites fabricated by ultrasonic cavitation-based solidification processing

Mg–6Zn/1.5%SiC nanocomposites were successfully fabricated by ultrasonic cavitation-based dispersion of SiC nanoparticles in Mg–6Zn alloy melt. As compared to un-reinforced Mg–6Zn alloy matrix, the mechanical properties of the nanocomposites including the tensile strength and yield strength of the Mg–6Zn/1.5%SiC nanocomposites were significantly higher; the good ductility of Mg–6Zn alloy matrix was retained. Nanoparticles were dispersed well though there were still some SiC microclusters in the microstructure. Also, the grain size of Mg–6Zn alloy was reduced considerably by the addition of 1.5%SiC nanoparticles.     

Power and gas pressure effects on properties of amorphous In–Ga–ZnO films by magnetron sputtering

Amorphous In–Ga–ZnO thin films were deposited on quartz glass substrate at room temperature utilizing radio frequency magnetron sputtering technique. Sputtering power and oxygen flow rate effects on the physical properties of the In–Ga–ZnO films were systematically investigated. It is shown the film deposition rate and the conductivity of the In–Ga–ZnO films increased with the sputtering power. The as-grown In–Ga–ZnO films deposited at 500 W exhibited the Hall mobility of 17.7 cm²/Vs. Average optical transmittance of the In–Ga–ZnO films is greater than 80% in the visible wavelength. The extracted optical band gap of the In–Ga–ZnO films increased from 3.06 to 3.46 eV with increasing the sputtering power. The electrical properties of the In–Ga–ZnO films are greatly dependent on the O₂/Ar gas flow ratio and post-growth annealing process. Increasing oxygen flow rate converted the In–Ga–ZnO films from semiconducting to semi-insulating, but the resistivity of the films was significantly reduced after being annealed in vacuum. Both the as-grown and annealed In–Ga–ZnO films show n-type electrical conductivity.