Structural and optical properties of Co-doped ZnO nanocrystallites prepared by a one-step solution route

Zinc oxide (ZnO) nanocrystallites with different Co-doping levels were successfully synthesized by a simple one-step solution route at low temperature (95 °C) in this study. The structure and morphology of the samples thus obtained were characterized by XRD, EDS, XPS and FESEM. Results show that cobalt ions, in the oxidation state of Co²⁺, replace Zn²⁺ ions in the ZnO lattice without changing its wurtzite structure. The dopant content varies from 0.59% to 5.39%, based on Co-doping levels. The pure ZnO particles exhibit well-defined 3D flower-like morphology with an average size of 550 nm, while the particles obtained after Co-doping are mostly cauliflower-like nanoclusters with an average size of 120 nm. Both the flower-like pure ZnO and the cauliflower-like Co:ZnO nanoclusters are composed of densely arrayed nanorods. The optical properties of the ZnO nanocrystallites following Co-doping were also investigated by UV–Visible absorption and Photoluminescence spectra. Our results indicate that Co-doping can change the energy-band structure and effectively adjust the luminescence properties of ZnO nanocrystallites.     

Experimental verification of enhanced electromagnetic field intensities at the photonic stop band edge of 3D polystyrene photonic crystals using Z-Scan technique

Enhancement of nonlinear absorption of polystyrene (PS) was investigated using 3D PS photonic crystals (PCs) with Z-scan technique. The Z-scan experiment was carried out at 532 nm in the picosecond (ps) regime. The transmittance of the PC was found to get modified because of the nonlinear absorption of PS particularly when 532 nm is near the photonic stop band (PSB) edge of PC. Calculations show that the field gets enhanced by 1.4 times the input field intensity within the crystal when the 532 nm wavelength falls at the PSB edge while keeping the crystal at an angle of 35°.     

Synthesis of defect-rich, (001) faceted-ZnO nanorod on a FTO substrate as efficient photocatalysts for dehydrogenation of isopropanol to acetone

Highly oriented ZnO nanorod was successfully synthesised on Ag nanoseed coated FTO substrate via a microwave hydrolysis approach. It was found that the morphology and the optical properties of the ZnO nanorod are strongly influenced by the power of the microwave irradiation used during the growth process. The aspect ratio of the nanorods changed from high to low with the increasing of microwave power. It was also found that the optical band gap of the ZnO nanorod red shifted with the increasing of the microwave power, reflecting an excellent tune ability of the optical properties of ZnO nanorods. The photocatalytic activity of these unique nanorod was evaluated by a dehydrogenation process of isopropanol to acetone in the presence of ZnO nanorod. It was found that the ZnO nanorod exhibited an excellent catalytic performance by showing an ability to accelerate the production of 0.031 mol L⁻¹ of acetone within only 35 min or 0.9 mmol L⁻¹ min⁻¹ from isopropyl alcohol dehydrogenation. It was almost no conversion from isopropyl alcohol when ZnO nanorods was absence during the reaction. In this report, a detailed mechanism of ZnO nanorod formation and the relationship between morphology and optical energy band gap are described.     

The effects of liquid height/volume,initial concentration of reactant and acoustic power on sonochemical oxidation

Even though much knowledge on acoustic cavitation and its application has been accumulated over the past decades, further research is still required to develop industrial uses of acoustic cavitation. It is because the available information is mainly based on small-scale sonoreactors and the design and optimization of sonoreactors for large-scale applications have not been widely studied. In this study, the effects of liquid height/volume, initial concentration of the reactant and input acoustic power on sonochemical oxidation reactions including iodide ion oxidation, As(III) oxidation, and hydrogen peroxide generation were investigated using a 291 kHz sonoreactor with various liquid height/volumes (50, 100, 200, 300, 500, and 1000 mL) and input powers (23, 40, and 82 W). As the liquid height/volume and the input power changed, the power density varied from 23 to 1640 W/L and the maximum cavitation yields of triiodide ion for 23, 40, and 82 W were observed at 0.05, 0.1, and 0.2/0.3 L, respectively. It was found that low power was more effective for the small volume and the large volume required high power level and the moderate power density, approximately 400 W/L, was suggested for the sonochemical oxidation of iodide ion in the 291 kHz sonoreactor in this study. Similar results were observed in the generation of hydrogen peroxide and the sonochemical oxidation of As(III) to As(V). It was also revealed that KI dosimetry could be applicable for the estimation of the sonochemical reactions of non-volatile compounds such as As(III).     

Microstructure and characterization of Al-doped ZnO films prepared by RF power sputtering on Al and ZnO targets

Al-doped zinc oxide (AZO) transparent conductive films were prepared on a glass substrate using a magnetron sputtering system with a pure zinc oxide (ZnO) target and a pure Al target sputtered using radio frequency (RF) power. The RF power was set at 100 W for the ZnO target and varied from 20 to 150 W for the Al target. The morphology of the thin films was examined by field-emission scanning electron microscope (FE-SEM), and their composition was analyzed by the equipped energy-dispersive X-ray spectroscopy (EDS). The cross section of the films determined through FE-SEM indicated that their thickness was around 650 nm. EDS analysis revealed that the Al-dopant concentration of the AZO films increased in the following order: 0.85 at.% (20 W) < 1.60 at.% (40 W) < 3.52 at.% (100 W) < 4.34 at.% (150 W). Analysis of the films using X-ray diffractometer (XRD) indicated that all films had a wurtzite structure with a texture of (0 0 2). High-resolution transmission electron microscopy (HRTEM) revealed a number of defects in the films, such as stacking faults and dislocations. Ultraviolet photoelectron spectroscopy (UPS) was used to estimate the optical energy gap (E_g) for the AZO thin films. The energy gap increases from 3.39 to 3.58 eV as the RF power applied to the Al target increase. The electrical resistivity of the films decreased from 3.43 × 10^?2 Ω cm to 3.29 × 10^?3 Ω cm as the RF power increased from 20 to 150 W when a four-point probe was used to investigate. Atomic force microscope (AFM) revealed that the surface roughness of the films increased with increasing RF power. The average optical transmittance of the films was determined by UV–visible spectrometer. The films are suitable for use as transparent conductive oxide films in the optoelectronic industry. A decrease in the electrical resistivity of the film with increasing Al-dopant concentration was ascribed to an increase in the carrier concentration and density of stacking faults in the films.     

The study of structure and optoelectronic properties of ZnS and ZnO films on porous silicon substrates

ZnS and ZnO films were prepared on porous silicon (PS) substrates with the same porosity by pulsed laser deposition (PLD), and the structural, optical and electrical properties of ZnS and ZnO films on PS were investigated at room temperature by X-ray diffraction (XRD), scanning electron microscope (SEM), optical absorption measurement, photoluminescence (PL) and I–V characteristic studies. The prepared ZnS was obtained in the cubic phase along β-ZnS (1 1 1) orientation which showed a perfect match with the earlier report while ZnO films were obtained in c-axis orientation. There appeared some cracks in the surface of ZnS and ZnO films due to the roughness of PS substrates. Luminescence studies of ZnS/PS and ZnO/PS composites indicated room temperature emission in a broad, intense, visible photoluminescence band, which cover the blue emission to red emission, exhibiting intensively white light emission. Based on the I–V characteristic, ZnS/PS heterojunction exhibited the rectifying junction behavior, while the I–V characteristic of ZnO/PS heterostructure was different from that of the common diode, whose reverse current was not saturated.     

Studies on structural and magnetic properties of Co-doped pyramidal ZnO nanorods synthesized by solution growth technique

Large-area arrays of highly oriented Co-doped ZnO nanorods with pyramidal hexagonal structure are grown on silica substrates by wet chemical decomposition of zinc–amino complex in an aqueous medium. In case of undoped ZnO with an equi-molar ratio of Zn²⁺/hexamethylenetetramine (HMT), highly crystalline nanorods were obtained, whereas for Co-doped ZnO, good quality nanorods were formed at a higher Zn²⁺/HMT molar ratio of 4:1. Scanning electron microscope (SEM) studies show the growth of hexagonal-shaped nanorods in a direction nearly perpendicular to the substrate surface with a tip size of ～50 nm and aspect ratio around 10. The XRD studies show the formation of hexagonal phase pure ZnO with c-axis preferred orientation. The doping of Co ions in ZnO nanorods was confirmed by observation of absorption bands at 658, 617 and 566 nm in the UV–vis spectra of the samples. The optical studies also suggest Co ions to be present both in +2 and +3 oxidation states. From the photoluminescence studies, a defect-related emission is observed in an undoped sample of ZnO at 567 nm. This emission is significantly quenched in Co-doped ZnO samples. Further, the Co-doped nanorods have been found to show ferromagnetic behavior at room temperature from vibrating sample magnetometer (VSM) studies.     

The role of torsional modes in the electronic absorption spectrum of acetone

The electronic absorption spectrum of acetone is revisited to evaluate the role of hot bands due to low lying torsional modes in the assignment of vibronic transitions. The UV–VUV photoabsorption spectrum of acetone is recorded in the energy region 3.5–11.8 eV at a resolution of ～4 meV at 4 eV and ～10 meV at 10 eV using synchrotron radiation. The absorption spectrum is dominated by richly structured Rydberg series (ns, np and nd) converging to the first ionization potential of acetone at 9.708 eV. Careful consideration of hot band contributions from torsional modes and symmetry selection rules have resulted in an improved set of vibronic assignments as compared to earlier room temperature work. Revised quantum defect values for some of the Rydberg transitions and a few new assignments in the nd series are also reported in this paper.     

The effect of ultrasonic irradiation on the structure,morphology and photocatalytic performance of ZnO nanoparticles by sol-gel method

In this research, the effect of ultrasonic irradiation power (0, 75, 150 and 200 W) and time (0, 5, 15 and 20 min) on the structure, morphology and photocatalytic activity of zinc oxide nanoparticles synthesized by sol-gel method was investigated. Crystallographic structures and the morphologies of the resultant powders were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns showed that ZnO samples were crystallized in their pure phase. The purity of samples was increased by increasing the ultrasonic irradiation power and time. Not only did ultrasonic irradiation unify both the structure and the morphology, but also it reduced the size and prohibited particles from aggregation. The optical behavior of the samples was studied by UV–vis spectroscopy. Photocatalytic activity of particles was measured by degradation of methyl orange under radiation of ultraviolet light. Ultrasound nanoparticles represented higher degradation compared to non-ultrasound ones.     

Disorder driven optical processes in nanocrystalline ZnO

A systematic study on the modification of optical properties in mechanically milled ZnO powder has been reported here. The average grain size of the powder becomes ～20 nm within 4 h of milling. Fluctuations of average grain size have been noticed at the initial stage of milling (within 15 min). Changes in grain morphology with milling have also been noticed in scanning electron micrographs of the samples. Room temperature optical absorption data shows a systematic red shift of absorption band edge (～3.25 eV). The band tail parameter (extracted from the optical absorption just below the band edge) follows a simple exponential relation with the inverse of the average grain size. Significant increase of the band tail parameter has been noticed at low grain size regime. It has been analyzed that high values of band tail parameter is a representative of V_Zn–V_O type divacancy clusters. Room temperature photoluminescence spectra show decrease (except for 120 min milling) of band edge emission intensity with increase of milling time. Subsequent decrease of sub-band edge emission is, however, less prominent. The variation of PL intensity ratio (intensity at band edge peak with that at 2.3 eV) follows simple exponential decrease with the increase of band tail parameter. This indeed shows that band edge emission in ZnO is related with the overall disorder in the system, not grain size induced only.     

Performance improvement of ZnO/P3HT hybrid UV photo-detector by interfacial Au nanolayer

In this study, a hybrid ultraviolet (UV) photo detector comprising of hydrothermally grown highly oriented Zinc Oxide nanorod arrays (ZnO NRAs) and Poly(3-hexylthiophene-2,5-diyl) (P3HT) as an active layer was fabricated and characterized. These hybrid photo detectors demonstrated a high rectification ratio (∼117) and responsivity of 10.7 A/W at −2  V under incident light of wavelength 325 nm. Further to investigate the effect of surface plasmon property of metal nanoparticles on the performance of hybrid UV photo detectors, ZnO NRAs were capped with dc sputtered gold (Au) metal nanolayer (∼5 nm) at the ZnO-P3HT interface, prior to coating P3HT layer on top of it. It was found out that upon Au coating the absorption of the ZnO was enhanced partly in the ultraviolet and visible region. In consequence the rectification ratio and responsivity of the hybrid photo detector was enhanced drastically from 117 to 1167 and 10.7 to 17.7 A/W respectively. Interestingly the reduction in dark current was observed on Au coating and it was revealed that Au nanoparticles play a key role in enhancing the performance of the hybrid photo detectors.     

Structural and photoluminescence investigation on the hot-wire assisted plasma enhanced chemical vapor deposition growth silicon nanowires

High density of silicon nanowires (SiNWs) were synthesized by a hot-wire assisted plasma enhanced chemical vapor deposition technique. The structural and optical properties of the as-grown SiNWs prepared at different rf power of 40 and 80 W were analyzed in this study. The SiNWs prepared at rf power of 40 W exhibited highly crystalline structure with a high crystal volume fraction, X_C of ～82% and are surrounded by a thin layer of SiO_x. The NWs show high absorption in the high energy region (E>1.8 eV) and strong photoluminescence at 1.73 to 2.05 eV (red–orange region) with a weak shoulder at 1.65 to 1.73 eV (near IR region). An increase in rf power to 80 W reduced the X_C to ～65% and led to the formation of nanocrystalline Si structures with a crystallite size of <4 nm within the SiNWs. These NWs are covered by a mixture of uncatalyzed amorphous Si layer. The SiNWs prepared at 80 W exhibited a high optical absorption ability above 99% in the broadband range between 220 and ～1500 nm and red emission between 1.65 and 1.95 eV. The interesting light absorption and photoluminescence properties from both SiNWs are discussed in the text.     

Structure of nanocrystalline ZnO up to 85 GPa

The structure of nanocrystalline and bulk polycrystalline ZnO were examined up to 85 GPa and 50 GPa, respectively using synchrotron X-rays and diamond anvil cells at ambient conditions. The transition from the wurtzite to the rock salt phase in the nano-ZnO takes place at 10.5 GPa; this transition pressure is 1.5 GPa higher than in bulk ZnO. A large volume collapse of about 17.5% is observed during the transition in both systems. The rocksalt phase is stable and no structural transitions are observed for both compounds at higher pressures up to the experimental limit. On decompression the rocksalt phase is found to co-exist with the wurtzite phase at ambient conditions for the nano-ZnO.     

Epitaxial ZnO thin films grown by pulsed electron beam deposition

In this work, the pulsed electron beam deposition method (PED) is evaluated by studying the properties of ZnO thin films grown on c-cut sapphire substrates. The film composition, structure and surface morphology were investigated by means of Rutherford backscattering spectrometry, X-ray diffraction and atomic force microscopy. Optical absorption, resistivity and Hall effect measurements were performed in order to obtain the optical and electronic properties of the ZnO films. By a fine tuning of the deposition conditions, smooth, dense, stoichiometric and textured hexagonal ZnO films were epitaxially grown on (0001) sapphire at 700 °C with a 30° rotation of the ZnO basal plane with respect to the sapphire substrate. The average transmittance of the films reaches 90% in the visible range with an optical band gap of 3.28 eV. Electrical characterization reveals a high density of charge carrier of 3.4 × 10¹⁹ cm^?3 along with a mobility of 11.53 cm²/Vs. The electrical and optical properties are discussed and compared to ZnO thin films prepared by the similar and most well-known pulsed laser deposition method.     

Experimental investigation of conical bubble structure and acoustic flow structure in ultrasonic field

The objective of this paper is to investigate the transient conical bubble structure (CBS) and acoustic flow structure in ultrasonic field. In the experiment, the high-speed video and particle image velocimetry (PIV) techniques are used to measure the acoustic cavitation patterns, as well as the flow velocity and vorticity fields. Results are presented for a high power ultrasound with a frequency of 18 kHz, and the range of the input power is from 50 W to 250 W. The results of the experiment show the input power significantly affects the structures of CBS, with the increase of input power, the cavity region of CBS and the velocity of bubbles increase evidently. For the transient motion of bubbles on radiating surface, two different types could be classified, namely the formation, aggregation and coalescence of cavitation bubbles, and the aggregation, shrink, expansion and collapse of bubble cluster. Furthermore, the thickness of turbulent boundary layer near the sonotrode region is found to be much thicker, and the turbulent intensities are much higher for relatively higher input power. The vorticity distribution is prominently affected by the spatial position and input power.     

Room temperature near-field photoluminescence of zinc-blend and wurtzite ZnO structures

Near-field photoluminescence (PL) was measured from ZnO film, composed of nanocrystallites with zinc-blend (ZB) and wurtzite (W) structures, on a sapphire (0 0 0 1) substrate at room temperature (RT). The size of nanocrystallites was in the range of 30–50 nm. Using a fiber probe with aperture size of 80 nm, two near-field emission peaks attributed to one ZB and one W structures were observed. The difference in the emission energies was 0.10 eV close to the calculated bandgap difference between ZB and W structures. The intensity of emission peak from ZB structure with lower energy was stronger than that from W structure, which is supposed to be resulted from the quenched excitonic effect of W structure.     

Influence of the ZnO nanoparticle sizes and morphology on the photoinduced light reflectivity

We have established a principal possibility of changes of the light reflectivity at the wavelength of 633 nm (He–Ne laser) under influence of the external laser light. The changes are very sensitive to the wavelength of the photoinduced laser. We have chosen two types of the photoinduced lasers: UV nitrogen 7 ns laser at wavelength 371 nm heating near the absorption edge and the 10 ns 1064 nm Nd:YAG laser with wavelength 1064 nm. The power dependences of the reflectivity were studied. Possible explanation of the observed effects is presented following the conception of the nano-trapping levels. These results have been obtained from two ZnO thin films prepared from principally different deposition parameters leading to different particle features and morphologies.     

Structural and optical properties of chromotrope 2R thin films of different thicknesses

Chromotrope 2R (CHR) films of different thicknesses have been prepared using spin coater. The material has been characterized using FT-IR, DTA and X-ray diffraction. The XRD of the material in powder and thin film forms showed polycrystalline structure with triclinic phase. Preferred orientation at the (1 1 4) plane is observed for the deposited films. Initial indexing of the XRD pattern was performed using “Crystalfire” computer program. Miller indices, h k l, values for each diffraction line in X-ray diffraction (XRD) spectrum were calculated and indexed for the first time. The DTA thermograms of CHR powder have been recorded in the temperature range 25–350 °C with different heating rates. The spectra of the infra-red absorption allow characterization of vibration modes for the powder and thin film. The effect of film thickness on the optical properties has been studied in the UV-visible-NIR regions. The films show high transmittance exceeding 0.90 in the NIR region λ > 800 nm. The intensity of the absorption peaks for λ < 800 nm are enhanced as the film thickness increase. The absorption bands are attributed to the (π–π*) and (n–π*) molecular transitions. The optical properties have been analyzed according to the single-oscillator model and the dispersion energy parameters as well as the free charge carrier concentration have been determined. The optical energy gap as well as the oscillator strength and electric dipole strength have been calculated.     

Spin coating-pyrolysis derived highly c-axis-oriented ZnO layers pre-fired at various temperatures

Transparent ZnO layers were prepared on silica glass substrates by the spin coating-pyrolysis process. As-deposited films were pre-fired at 250 °C for 60 min, at 350 °C for 30 min, and at 500 °C for 10 min, followed by heat treatment at 900 °C for 30 min in air. The ZnO films were analyzed by high resolution X-ray diffraction, field emission-scanning electron microscopy, scanning probe microscopy, and ultraviolet–visible–near infrared spectrophotometry. (0 0 2)-oriented ZnO films were obtained by pre-firing at 350 °C and at 500 °C. All the ZnO films exhibited a high transmittance, above 80%, in the visible region, and showed a sharp fundamental absorption edge at 0.38–0.40 μm. The most highly c-axis-oriented ZnO with a homogeneous surface was observed at a pyrolysis temperature of 350 °C.     

Fault detection of antenna arrays using infrared thermography

A fast and easy method for fault detection in antenna arrays using infrared thermography is presented. A thin, minimally perturbing, microwave absorption screen made of carbon loaded polymer is kept close in front of the faulty array. Electromagnetic waves falling on the screen increase its temperature. This temperature profile on the screen is identical to electric field intensity profile at the screen location. There is no temperature rise observed on the screen corresponding to non-radiating (faulty) elements and hence can be easily detected by IR thermography. The array input power is modulated at a low frequency which permits thermography to detect even weak fields. It also improves the resolution of thermal images. The power fed to the array is only 30 dBm. In order to show the utility of this technique, an example of 14 GHz 4 × 4 patch antenna array is given. The simulations are carried in CST Microwave Studio 2013. A good agreement between simulation and experimental results is observed.