Synthesis,structural and optical characterization of Ni-doped ZnO nanoparticles

Nanocrystalline Zn_1−x Ni _x O (x = 0.00, 0.02, 0.04, 0.06, 0.08) powders were synthesized by a simple sol–gel autocombustion method using metal nitrates of zinc, nickel and glycine. Structural and optical properties of the Ni-doped ZnO samples annealed at 800 °C are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis using X-rays (EDAX), UV–visible spectroscopy and photoluminescence (PL). X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a hexagonal wurtzite structure and secondary phase (NiO) was observed with the sensitivity of XRD measurement with the increasing nickel concentration (x ≥ 0.04). The lattice constants of Ni-doped ZnO nanoparticles increase slightly when Ni²⁺ is doped into ZnO lattice. The optical absorption band edge of the nickel doped samples was observed above 387 nm (3.20 eV) along with well-defined absorbance peaks at around 439 (2.82 eV), 615(2.01 eV) and 655 nm (1.89 eV). PL measurements of Ni-doped samples illustrated the strong UV emission band at ~3.02 eV, weak blue emission bands at 2.82 and 2.75 eV, and a strong green emission band at 2.26 eV. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

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.     

Tuning the band gap of ZnO nanoparticles by ultrasonic irradiation

In this present paper, we report the tunability of ZnO nanoparticles by ultrasonic irradiation. Different sized ZnO nanoparticles viz. 2.58–2.97 nm have been synthesized with variation of ultrasonic irradiation time 75–270 min in presence of Histidine as capping agent. UV and visible spectroscopy study revealed that as ultrasonic irradiation time increases, there is increase in amount of formed ZnO nanoparticles and also there is red shift in absorption edge. This confirms the tunability of bandgap of histidine capped ZnO nanoparticles with ultrasonic irradiation. Growth mechanism for controlling the size of ZnO nanoparticles are also discussed.     

Structure and photoluminescence of SiC/ZnO nanocomposites prepared by radio frequency alternate sputtering

SiC/ZnO nanocomposites were prepared by radio frequency alternate sputtering followed by annealing in N₂ ambient. Well-crystallized ZnO matrix was obtained after annealed at 750 °C according to X-ray diffractometer patterns. Transmission electron microscopy analyses indicated that the SiC thin layer aggregated to form SiC nanoclusters with the average size of 7.2 nm when the annealing temperature was 600 °C. When the annealing temperatures increased above 900 °C, some of the SiC nanoclusters changed into SiC nanocrystals and surfacial atoms of the SiC nanoparticles were surrounded by a layer of SiO _x (x ≤ 2) according to the Fourier transform infrared spectrums. The SiC/ZnO nanocomposites annealed at 750 °C exhibit strong photoluminescence bands ranging from 250 to 600 nm. UV light originates from the near band edge emission of ZnO and the blue emission peaked at around 465 nm (2.7 eV) may be due to the formation of emission centers caused by the defects in Si–O network, while the green-emission peak at around 550 nm (2.3 eV) may be attributed to the deep level recombination luminescence caused by the vacancies of oxygen and zinc.     

Morphology controlled synthesis of ZnO nanostructures by varying pH

ZnO nanostructures have been synthesized in a controlled manner by varying the pH of the precursor solution using hydrothermal technique. The morphological changes of the prepared ZnO nanostructures have been investigated in the range of pH 5–10. Radial hexagonal rod-like shape is formed at lower pH values of 5 and 6 whereas, flower-like shape is obtained for higher pH values of 9 and 10. Flake-like structure is observed at moderate pH of 8. The prepared ZnO nanostructures have been characterized using X-ray diffraction technique (XRD), energy dispersive X-ray analysis, scanning electron microscope and FTIR spectroscopy. XRD results show that the prepared ZnO nanostructures exhibit hexagonal wurtzite structure. The growth mechanism suggests that the supersaturation of the precursor results in various nucleation habits, which induce the formation of ZnO nanostructures with different morphologies. UV–Vis spectroscopy and photoluminescence were applied to study the optical properties. The photoluminescence spectrum demonstrated two emission bands, a near band edge emission in the UV region and a strong deep band emission in the visible region. The change in pH from 5 to 10 results in band gap variations of 3.47–3.97 eV and blue-shift in the peak emission of visible PL from 560 to 460 nm.     

ZnO nanocrystalline thin films: a correlation of microstructural,optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol–gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 °C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60–80 nm in size is really an aggregate of many small crystallites of around 10–20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10⁻⁵–10⁻⁶ (Ω cm)⁻¹. The optical study showed that the spectra for all samples give the transparency in the visible range.     

Nanostructured ZnO hexagons and optical properties

We report the solvothermal synthesis of nanostructured ZnO hexagons by hydrothermal method via intermediate zinc adipate. The intermediate zinc adipate was obtained using precursors zinc acetate and adipic acid in aqueous and organic medium. Detailed XRD analysis of the zinc adipate was studied for the first time. Thermal study of intermediate showed the formation of ZnO at 400 °C. XRD study demonstrated the existence of wrutzite ZnO of high degree of crystallinity with crystallite size in the range of 20–25 nm. Scanning Electron Microscopy (SEM) showed distinguished morphology in different medium. Transmission Electron Microscopy (TEM) demonstrated nanostructured ZnO hexagons with average size 25–50 nm. The band gap for aqueous and organic mediated ZnO was found to be 3.24 and 3.26 eV, respectively. The band gap obtained is higher than the bulk ZnO, which implies nanocrystalline nature of the material.     

Preparation of polymorphic ZnO with strong orange luminescence

Polymorphic ZnO has been prepared by a solution method at low temperature (40–90 °C) and the product has been characterized by transmission electron microscopy, UV–vis absorption, and photoluminescence spectroscopy. It is found that the morphology and microstructure of ZnO can be tuned by varying the growth temperature and crystallization condition. The as-synthesized product exhibits narrowed band gap and strong orange luminescence at 620 nm, which may arise from the interstitial oxygen ion defect introduced into ZnO in the solution growth process.     

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.     

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.     

Fabrication of ZnO tetrapods on silicon substrate by thermal evaporation

Large-scale ZnO tetrapods have been fabricated on silicon substrate by a simple thermal evaporation method at 700 °C without vapor transportation and characterized by FESEM, XRD, Micro-Raman, and PL, respectively. FESEM images indicate that the length of tetrapod arm is about 3–4 μm, and the diameter of the tip is about 50 nm. XRD and Raman spectrum reveal that ZnO tetrapods are highly pure hexagonal wurtzite structure. The PL spectrum indicates that the ZnO tetrapods have strong green emission at 510 nm.     

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.     

The structural and optical properties of ZnO nanorods via citric acid-assisted annealing route

ZnO nanorods with diameters ranging from 25 to 88 nm and with length up to 1 μm were obtained via citric acid-assisted annealing route. The sample was characterized by X-ray diffraction, field-emission scanning electron microscopy (FE-SEM), Raman spectrometer, FTIR spectrophotometer, ultraviolet visible (UV–VIS) spectroscopy, and photoluminescence (PL) spectroscopy. It demonstrates that the sample is composed of ZnO with hexagonal structure and the ZnO nanorods are of excellent optical quality.     

Vertically aligned nanocrystalline Cu–ZnO thin films for photoelectrochemical splitting of water

Cu-incorporated nanocrystalline ZnO thin films were deposited on glass substrate by sol–gel. To a solution of zinc acetate 2-hydrate in dimethyl formamide, calculated quantities of copper acetate were added. The clear solution, obtained after 2 h of continuous stirring, was coated on ITO plates. Pre-annealing at 250 °C was followed by sintering at 400, 500, and 600 °C. XRD analysis revealed dominant evolution of hexagonal ZnO with a possible simultaneous growth of meta-stable cubic ZnO. AFM and SEM analysis indicated preferential growth of nanocrystallites along c-axis. Optical characterization led to two prominent absorption thresholds in the UV region; one matching with the band gap of bulk ZnO and the second at slightly higher energy, suggesting quantum confinement effect in nanocrystallites. Cu incorporation influenced the two band gap energies differently. Photoelectrochemical splitting of water using 1% at. Cu–ZnO film sintered at 600 °C resulted in 141% gain in photocurrent at zero bias.     

Growth and properties of ZnO nanowires synthesized by a simple hydrothermal method

Hexagonal ZnO nanowires were synthesized on pre-seeded silicon (100) substrates by a simple hydrothermal method at a relatively low temperature of 95 °C without any catalyst or template. The pre-seeded layer was produced using the sol–gel spin coating technique with 1 M zinc acetate in ethanol and ethanolamine. The structural properties of the nanowires were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD pattern indicated that the as-grown ZnO nanowires had the single-phase wurtzite structure, formed along the c-axis. SEM revealed that the nanostructure thin film had wire textures and the synthesis processes importantly influence the final size and shape of the ZnO nanowires. High-resolution transmission electron microscopy (HRTEM) provided further insight into the structure of ZnO nanostructures. The obtained HRTEM image was of the tip of an individual nanowire. The ZnO nanowires highly preferentially grew in the (002) crystal plane. The lattice spacing between adjacent (002) lattice planes was calculated to be 0.52 nm. The optical characteristics of the nanowires were determined from cathodoluminescence (CL) spectra. The CL revealed a fairly high surface state density of ZnO nanowires that grew at reaction concentrations of 0.01–0.25 M.     

Photoresponse of n -ZnO/ p -Si heterojunction towards ultraviolet/visible lights: thickness dependent behavior

A series of n-ZnO/p-Si thin film heterojunctions have been fabricated by a low cost sol–gel technique for different ZnO film thicknesses and the dark as well as photo current–voltage (I–V) characteristics have been investigated in details. The heterojunction with ZnO thickness of 0.46 μm shows the best diode characteristics in terms of rectification ratio, I _F/I _R = 5.7 × 10³ at 5 V and reverse leakage current density, J _R = 7.6 × 10⁻⁵ A cm⁻² at −5 V. From the photo I–V curves and wavelength dependent photocurrent of the heterojunctions, it is found that the junction with 0.46 μm ZnO thickness shows the highest sensitivity towards both UV and visible lights.     

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.     

Analysis of growth parameters for hydrothermal synthesis of ZnO nanoparticles through a statistical experimental design method

Nanocrystalline ZnO particles were synthesized from an aqueous solution composed of zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and urea (H₂NCONH₂). A precipitating precursor, basic zinc carbonate (Zn₅(CO₃)₂(OH)₆), was first formed by hydrothermally treating the solution at 120 °C for 2–4 h. Nanocrystalline ZnO particles were then obtained by calcining the precursors at 350–650 °C for 0.5–2 h. The synthesis products were characterized using thermogravimetry–differential scanning calorimetry–mass spectrometry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. Based on the experimental results, a possible reaction mechanism for the ZnO formation was proposed. The effects of experimental parameters (namely, the hydrothermal treatment time, the calcination time, and the calcination temperature) on the characteristics of the resulting ZnO products (i.e., the crystalline size and the photoluminescence properties) were analyzed by the Taguchi method to attain the optimum synthesis conditions. By using the appropriate parameters derived from this method, we verified that the optimized synthesis provided a yield of ~70% and that the resulting ZnO particles possessed the characteristics of a ~25 nm crystalline size and a satisfactory photoluminescence property.     

Fluorescent dye encapsulated ZnO particles with cell-specific toxicity for potential use in biomedical applications

Fluorescein isothiocyanate (FITC)-encapsulated SiO₂ core-shell particles with a nanoscale ZnO finishing layer have been synthesized for the first time as multifunctional “smart” nanostructures. Detailed characterization studies confirmed the formation of an outer ZnO layer on the SiO₂–FITC core. These ~200 nm sized particles showed promise toward cell imaging and cellular uptake studies using the bacterium Escherichia coli and Jurkat cancer cells, respectively. The FITC encapsulated ZnO particles demonstrated excellent selectivity in preferentially killing Jurkat cancer cells with minimal toxicity to normal primary immune cells (18% and 75% viability remaining, respectively, after exposure to 60 μg/ml) and inhibited the growth of both gram-positive and gram-negative bacteria at concentrations ≥250–500 μg/ml (for Staphylococcus aureus and Escherichia coli, respectively). These results indicate that the novel FITC encapsulated multifunctional particles with nanoscale ZnO surface layer can be used as smart nanostructures for particle tracking, cell imaging, antibacterial treatments and cancer therapy.     

Strong yellow emission of ZnO hollow nanospheres fabricated using polystyrene spheres as templates

ZnO hollow nanospheres were fabricated using polystyrene (PS) microspheres as templates were demonstrated in this paper. The structures and morphologies of obtained products were characterized by XRD, FESEM and TEM. The results revealed that ZnO hollow nanospheres possess a hexagonal wurtzite structure with a diameter around 450–500 nm. Ultraviolet–visible (UV–vis) analysis showed that ZnO hollow nanospheres had high absorption in the ultraviolet region and low absorption in the visible region. Room temperature photoluminescence (PL) spectrum showed a weak UV emission at 380 nm and a strong and broad yellow emission centered at 550 nm. The formation mechanism of hollow structure was also investigated.