Characterization of luminescent chromophore obtained from silica spheres

Blue light emitting chromophores have been separated from silica spheres by soaking them into acetone for 120 days. The luminescent chromophores were not obtained from other solvents, including ether, methanol, ethanol, 2-propanol, chloroform and tetrahydrofuran. According to the Fourier transform infrared spectrum, the luminescent material is composed of C–OH, –CH₂, –CH₃, C=O, and Si–O–Si. UV–visible absorption peak of the chromophore is at 5.17 eV (240 nm). Field emission scanning electron microscope images show small cracks on the surface of aged spheres. The luminescence peak was at 2.81 eV (441 nm) for excitation energy between 3.88 and 3.35 eV and slightly shifted toward lower energy for excitation energy lower than 3.35 eV. The deconvoluted luminescent spectrum shows two emission bands at 3.08 and 2.74 eV, which are well-matched the oxygen deficient center model. Compared to the absorption peak (5.17 eV) and the emission peak (2.81 eV), large Stokes shift (2.36 eV) is observed.     

Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol

The aim of the study is to investigate the optical properties of spin-coated, highly transparent nanocomposite films of oleic acid modified ZnO (Zinc oxide) nanorods embedded in Polyvinyl alcohol (PVA) matrix. Pristine and oleic acid (OA) modified ZnO nanorods have been prepared by wet chemical synthesis and are characterized by X-ray diffraction, FESEM, TEM and FT–IR spectroscopy techniques. The optical properties of ZnO/PVA films are studied using UV–visible absorption and Photoluminescence (PL) spectroscopy. The results show that the optical absorption of the films in the UV region is quite high and more than 95% absorption is observed in films prepared from OA modified ZnO nanorods. The excellent UV absorption at around 300 nm offers prospects of applications of these films as efficient UV filters in this wavelength region. The PL spectrum of pristine ZnO nanorods shows almost white light emission whereas OA modified ZnO nanorods have a more intense peak centered in the blue region. The PL emission of OA modified ZnO/PVA film shows appreciable increase in intensity compared to the film obtained with pristine ZnO. The surface modification of ZnO by the polymer matrix removes defect states within ZnO and facilitates sharp near band edge PL emission at 364 nm.     

Magneto-optical properties of α-Fe2O3@ZnO nanocomposites prepared by the high energy ball-milling technique

Magnetic–fluorescent nanocomposites (NCs) with 10 wt% of α-Fe₂O₃ in ZnO have been prepared by the high energy ball-milling. The crystallite sizes of α-Fe₂O₃ and ZnO in the NCs are found to vary from 65 nm to 20 nm and 47 nm to 15 nm respectively as milling time is increased from 2 to 30 h. XRD analysis confirms presence of α-Fe₂O₃ and ZnO in pure form in all the NCs. UV–vis study of the NCs shows a continuous blue-shift of the absorption peak and a steady increase of band gap of ZnO with increasing milling duration that are assigned to decreasing particle size of ZnO in the NCs. Photoluminescence (PL) spectra of the NCs reveal three weak emission bands in the visible region at 421, 445 and 485 nm along with the strong near band edge emission at 391 nm. These weak emission bands are attributed to different defect – related energy levels e.g. Zn-vacancy, Zn interstitial and oxygen vacancy. Dc and ac magnetization measurements show presence of weakly interacting superparamagnetic (SPM) α-Fe₂O₃ particles in the NCs. ⁵⁷Fe-Mössbauer study confirms presence of SPM hematite in the sample milled for 30 h. Positron annihilation lifetime measurements indicate presence of cation vacancies in ZnO nanostructures confirming results of PL studies.     

Emission of Cu-related complexes in ZnO:Cu nanocrystals

Photoluminescence (PL), its temperature dependence, scanning electronic microscopy (SEM) and X ray diffraction (XRD) have been applied for the comparative study of varying the emission, morphology and crystal structure of ZnO and ZnO:Cu nanocrystals (NCs) versus technological routines, as well as the dependence of ZnO:Cu NC parameters on the Cu concentration. A set of ZnO and ZnO Cu NCs was prepared by the electrochemical (anodization) method at a permanent voltage and different etching durations with follows thermal annealing at 400 °C for 2 h in ambient air. The size of ZnO NCs decreases from 300 nm×540 nm down to 200 nm×320 nm with etching duration increasing. XRD study has confirmed that thermal annealing stimulates the ZnO oxidation and crystallization with the formation of wurtzite ZnO crystal lattice. XRD method has been used for monitoring the lattice parameters and for confirming the Cu doping of ZnO Cu NCs. In ZnO Cu NCs four defect related PL bands are detected with the PL peaks at 1.95–2.00 eV (A), 2.15-2.23  eV (B), 2.43–2.50 eV (C) and 2.61–2.69 eV (D). Highest PL intensities of orange, yellow and green emissions have been obtained in ZnO Cu NCs with the Cu concentration of 2.28 at%. At Cu concentration increasing (≥2.28 at%) the PL intensities of the bands A, B, C decrease and the new PL band peaked at 2.61–2.69 eV at 10 K appears in the PL spectrum. The variation of PL intensities for all PL bands versus temperature has been studied and the corresponding activation energies of PL thermal decay have been estimated. The type of Cu-related complexes is discussed using the correlation between the PL spectrum transformation and the variation of XRD parameters in ZnO Cu NCs.     

Photoluminescence studies of ZnO thin films on R-plane sapphire substrates grown by sol–gel method

Zinc oxide (ZnO) thin films on R-plane sapphire substrates were grown by the sol–gel spin-coating method. The optical properties of the ZnO thin films were investigated using photoluminescence. In the UV range, the asymmetric near-band-edge emission was observed at 300 K, which consisted of two emissions at 3.338 and 3.279 eV. Eight peaks at 3.418, 3.402, 3.360, 3.288, 3.216, 3.145, 3.074, and 3.004 eV, which respectively correspond to the free exciton (FX), bound exciton, transverse optical (TO) phonon replica of FX recombination, and first-order longitudinal optical phonon replica of FX and the TO (1LO+TO), 2LO+TO, 3LO+TO, 4LO+TO, and 5LO+TO, were obtained at 12 K. From the temperature-dependent PL, it was found that the emission peaks at 3.338 and 3.279 eV corresponded to the FX and TO, respectively. The activation energy of the FX and TO emission peaks was found to be about 39.3 and 28.9 meV, respectively. The values of the fitting parameters of Varshni's empirical equation were α=4×10^?3 eV/K and β=4.9×10³ K, and the S factor of the ZnO thin films was 0.658. With increasing temperature, the exciton radiative lifetime of the FX and TO emissions increased. The temperature-dependent variation of the exciton radiative lifetime for the TO emission was slightly higher than that for the FX emission.     

Band offsets at ZnO/SiC heterojunction: Heterointerface in band alignment

Pulsed laser deposited ZnO layers on 6H-SiC substrates showed the six-fold symmetry, indicating a two-dimensional epitaxial growth mode. X-ray photoelectron spectroscopy was employed to study the valence band discontinuity and interface formation in the ZnO/6H-SiC heterojunction. The valence band offset was measured to be 1.38 ± 0.28 eV, leading to a conduction band offset value of 1.01 ± 0.28 eV. The resulting band lineup in epitaxial ZnO/6H-SiC heterojunction is determined to be of staggered-type alignment.     

Photocatalytic degradation of ciprofloxacin drug in water using ZnO nanoparticles

We report the synthesis of nanostructure ZnO semiconductor with ～2.1 nm diameter using a chemical precipitation method. The resulting nanoparticles were characterized by X-ray diffraction analysis (XRD), Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The optical properties were investigated by UV–vis and fluorescence techniques. The absorption spectra exhibit a sharp absorption edge at ～334 nm corresponding to band gap of ～3.7 eV. The fluorescence spectra displayed a near-band-edge ultraviolet excitonic emission at ～410 nm and a green emission peak at ～525 nm, due to a transition of a photo-generated electron from the conduction band to a deeply trapped hole. The photocatalytic activity of the prepared ZnO nanoparticles has been investigated for the degradation of ciprofloxacin drug under UV light irradiation in aqueous solutions of different pH values. The results showed that the photocatalytic degradation process is effective at pH 7 and 10, but it is rather slow at pH 4. Higher degradation efficiency (～50%) of the drug was observed at pH 10 after 60 min. Photodegradation of the drug follows a pseudo-first-order kinetics.     

Does methanol produce a stable methoxy species on Ru(0001) at low temperatures?

Soft X-ray photoelectron spectroscopy (SXPS) and energy-scanned photoelectron diffraction (PhD) have been used to study the surface species produced by exposure of Ru(0001) to methanol at ~ 150 K. SXPS shows a single surface species is formed at sub-monolayer coverages with an O 1s peak binding energy of ~ 532.6 eV, 2.8 eV greater than that of chemisorbed atomic oxygen. O 1s PhD data from this species shows no significant modulations, in contrast to simulated PhD spectra from a methoxy species occupying a three-fold coordinated hollow site, as predicted by earlier density functional theory calculations, or atop or bridging sites. By contrast, PhD data from the O 1s of the atomic oxygen species in the Ru(0001)(2 × 1)–O phase are consistent with the oxygen atoms occupying ‘hcp’ hollow sites (above second-layer Ru atoms) at a RuO bondlength of 2.01 ± 0.02 Å, essentially identical to previous structure determinations of this phase. O 1s PhD recorded at normal emission from adsorbed CO are also consistent with the known CO atop adsorption species. We conclude that the methanol-derived surface molecular species is not methoxy in a well-defined local site on the surface, but is consistent with clusters of intact methanol identified in a recent infrared spectroscopy investigation.     

Strong violet emission from zinc oxide dumbbell-like microrods and nanowires

ZnO of different morphologies with controlled size and aspect ratio (l/d) such as dumbbell-like microrods, thick nanowires and thin nanowires were prepared by a hydrothermal method. Possible mechanisms for the formation of ZnO crystals with the different morphologies were discussed. Strong violet photoluminescence bands at～413 nm (3.0 eV) without band edge emission were observed from the dumbbell-like ZnO microrods and thick nanowires. Correspondingly, the thin nanowires showed a weak shoulder UV photoluminescence band at～390 nm. Such result indicates that the photoluminescence properties could be improved by the morphologies or aspect ratio (l/d) and the potential fabrication violet-light-emitting devices.     

Radioluminescence of synthetic quartz related to alkali ions

The radioluminescence (RL) of synthetic quartzes (GEMMA Quartz & Crystal Company) has been measured at room temperature. Some samples were treated by electrodiffusion (“sweeping”) in order to change the concentrations of alkali ions, mainly Li⁺ and Na⁺, which in quartz are known to be linked to Al ions, substitutional for Si ions.The RL emission spectra show evidence of a role of alkali ions in affecting some specific emissions. All the spectra could be analysed as composed of four bands in the blue and UV region. Specifically, the well known blue emission at around 470 nm was seen to be composed by two bands at 430 nm (2.86 eV) and at 485 nm (2.53 eV). Effects of irradiation, during the RL measurements, were clearly seen only in the “Li swept in” sample, namely an increase in the 485 nm band intensity and a decrease in the 430 nm band one. The previously reported UV emission was detected at 355 nm (3.44 eV) in all the samples, being the most intense band in the “swept out” sample. A further UV emission was detected at 315 nm (3.94 eV), more intense in untreated samples.Possible assignments of the detected emission bands are discussed in relation to the defects of quartz, specifically focusing on the Al centres that are most affected by sweeping procedures.     

Negative thermal quenching of the 3.338 eV emission in ZnO nanorods

We investigate the negative thermal quenching behavior of the 3.338 eV emission in ZnO nanorods. A correlation between the 3.338 eV and the 3.368 eV (surface exciton) emissions is determined from temperature-dependent photoluminescence. The activation energies of the 3.338 eV emission, obtained using an approximated multi-level model, indicate an trap state between the two surface exciton emissions. The present study demonstrates a nondestructive and easy method to understand the surface effects on the optical properties of semiconductor nanostructures.     

Comparative study on the effects of different annealing conditions on the surface morphology,crystallinity, and optical properties of ZnO micro/nanoparticle-based discs

The effects of annealing parameters on the surface morphology, crystallinity, and optical properties of ZnO disc were investigated. Variations in the annealing temperatures and gas flow rates were found to have a profound impact; grain growth was enhanced even at the low annealing temperature of only 400 °C. SEM and AFM revealed smooth and uniform grain growth after annealing treatment, especially at 800 °C. A unique secondary growth of ZnO nanoparticles and multilayer grain growth that have not been reported elsewhere were also observed. The annealing treatment was also found to improve grain crystallinity as illustrated by the lowering of intrinsic compressive stress based on the XRD lattice constant and FWHM data. The PL spectra of the M-Disc showed a huge band edge emission at 371–376 nm. In contrast, the N-Disc exhibited a dominant and broad visible PL emission in the green band with peaks at 519–533 nm. These peaks were attributed to a very high concentration of structural defects (oxygen vacancies and zinc/oxygen interstitials). The annealing conditions had a significant effect on the properties of ZnO. Increased percentage of oxygen in the O/Ar from 50% to 100% did not change the M-Disc spectra. However, the XRD pattern of the N-Disc revealed that the (0 0 2) peak intensity decreased, the position of the (1 0 1) peak slightly shifted toward a higher angle, and the FWHM of the (1 0 1) peak improved. The experimental results showed that thermal annealing could enhance the different properties of ZnO discs.     

Green synthesis of nanocomposites consisting of silver and protease alpha chymotrypsin

The synergy of ultrasonication and the exposure to light radiation was found to be necessary in the formation of nanocomposites of silver and a protease alpha chymotrypsin. The reaction was carried out in aqueous medium and the process took just less than 35 min. Ultrasonication alone formed very negligible number of nanoparticles of <100 nm size whereas light alone produced enough number but the size of the particles was >100 nm.The effects of pH (in the range of 3–5, 9–10), ultrasonication time periods (0–30 min), ultrasonication intensity (33–83 W cm^?2), energy of light radiation (short UV, long UV and Fluorescent light) and time period of exposure (5–60 min) to different light radiations were studied.The formation of nanocomposites under these effects was followed by surface plasmon resonance (SPR) spectra, dynamic light scattering (DLS), transmission electron microscopy (TEM). Ag–chymotrypsin nanocomposites of sizes ranging from 13 to 72 nm were formed using the synergy of ultrasonication and exposure to short UV radiation. Results show that ultrasonication promoted nuclei formation, growth and reduction of polydispersity by Ostwald ripening.     

High c-axis preferred orientation ZnO thin films prepared by oxidation of metallic zinc

Thin films of zinc oxide were grown on glass substrates by thermal oxidation. The metallic zinc films were thermally oxidized at different temperatures ranging from 300 to 600 °C to yield ZnO thin films. The structural property of the thin films was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The X-ray diffraction measurements showed that the films oxidized at 300 °C were not oxidized entirely, and the films deposited at 600 °C had better crystalline quality than the rest. When the oxidation temperature increased above 400 °C, the films exhibited preferred orientation along (002) and high transmittance ranging from 85% to 98% in vis–near-infrared band. Meanwhile, the films showed a UV emission at about 377 nm and green emission. With the increasing of oxidation temperature, the intensity of green emission peak was enhanced, and then decreased, disappearing at 600 °C, and the case of UV emission increased. Furthermore, a strong green emission was observed in the film sintered in pure oxygen atmosphere.     

Electronic core levels of hydroxyls at the surface of chromia related to their XPS O 1s signature: A DFT + U study

The Cr 2p and O 1s binding energy (BE) levels have been calculated by first principles methods for different models of hydroxylated (0001)-Cr₂O₃ surfaces. Several surface terminations have been considered. The calculations allow us to reproduce the O 1s shifts between O in oxide and OH groups. It is found that two main effects account for the OH binding energy shifts. On the one hand, the increased covalency of the O–H bond with respect to the Cr–O bond, lowers the electronic O (1s and 2p) energy, and in consequence the BE of the core levels (O 1s) are higher. On the other hand, the lower the OH coordination number, the higher the valence and core levels energy, and the lower the BE. Consequently, mono-coordinated hydroxyls have a binding energy near that of O^2? in the oxide (ΔBE_OH–O = ? 0.2–0.0 eV). Two-fold coordinated hydroxyls have a slightly higher BE (ΔBE_OH–O = + 0.3 eV). Three-fold coordinated OH groups have a higher binding energy (ΔBE_OH–O = + 0.6?0.7 eV), corresponding to that experimentally measured for OH groups. Finally, water adsorbed above OH groups exhibits a still higher BE (ΔBE_HOH–O = + 0.9–1.0 eV). The ΔBE are slightly under-estimated under the initial state approximation, and overestimated under the final state (Z + 1) approximation.     

Sonochemical synthesis of hierarchical ZnO nanostructures

This work is about fabrication of ZnO nanostructures (ZnO-NS) via a simple sonochemical method. The chemicals used for the synthesis of various shaped ZnO are Zn salt, sodium hydroxide and ammonia solution without other structure directing agent or surfactant needed. This method is feasible and green, as it does not require high temperature and/or highly toxic chemicals. The shape of the ZnO-NS can be tuned by adjusting the ultrasound energy dissipated via varying the ultrasonication time from 5 to 60 min. It was found that uniform ZnO nanorods with diameter around 50 nm were formed after 15 min of ultrasonication while flowerlike ZnO-NS was formed after 30 min. This method produces high quality ZnO-NS with controllable shapes, uniformity, and purity.     

Structural and optical properties of Mn-doped ZnO nanocrystalline thin films with the different dopant concentrations

The transparent nanocrystalline thin films of undoped zinc oxide and Mn-doped (Zn_1−xMn_xO) have been deposited on glass substrates via the sol–gel technique using zinc acetate dehydrate and manganese chloride as precursor. The as-deposited films with the different manganese compositions in the range of 2.5–20 at% were pre-heated at 100 °C for 1 h and 200 °C for 2 h, respectively, and then crystallized in air at 560 °C for 2 h. The structural properties and morphologies of the undoped and doped ZnO thin films have been investigated. X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to examine the morphology and microstructure of the thin films. Optical properties of the thin films were determined by photoluminescence (PL) and UV/Vis spectroscopy. The analyzed results indicates that the obtained films are of good crystal quality and have smooth surfaces, which have a pure hexagonal wurtzite ZnO structure without any Mn related phases. Room temperature photoluminescence is observed for the ZnO and Mn-doped ZnO thin films.     

Preferred orientation of ZnO nanoparticles formed by post-thermal annealing zinc implanted silica

High quality zinc oxide nanoparticles with (002) preferred orientation were prepared by post-thermal annealing zinc implanted silica at 700 °C using two methods. One method was annealing zinc implanted silica at 700 °C for 2 h in oxygen ambient; the other method was sequentially annealing zinc implanted silica at 700 °C in nitrogen and oxygen ambient for 1 h, respectively. X-ray diffraction (XRD), absorption and microphotoluminescence (micro-PL) results indicated that the latter method could create high quality ZnO nanoparticles with (002) preferred orientation and narrow size-distribution. X-ray photoelectron spectra (XPS) showed the formation of ZnO nanoparticles on a silica surface, where the ZnO nanoparticle content increased with increasing oxidation time in an oxygen environment. The processes of the transformation from Zn to ZnO are discussed.     

Optical properties and structural characteristics of ZnO thin films grown on a-plane sapphire substrates by plasma-assisted molecular beam epitaxy

We investigated structural and optical properties of ZnO thin films grown on (112?0) a-plane sapphire substrates using plasma-assisted molecular beam epitaxy. Negligible biaxial stress in ZnO thin films is due to the use of (112?0) a-plane sapphire substrates and slow substrate cooling. The 14 K photoluminescence spectrum shows a blueshift of energy positions compared with ZnO single crystal. A donor with binding energy of 43 meV and an acceptor with binding energy of ～170 meV are identified by well-resolved photoluminescence spectra. A characteristic emission band at 3.320 eV (so-called A-line) is studied. Based on analysis from photoluminescence spectra, the origin of the A-line, it seems, is more likely an (e, A°) transition, in which defect behaves as an acceptor. The room-temperature photoluminescence is dominated by the FX at 3.307 eV, which is an indication of strongly reduced defect density in ZnO thin films.     

Characteristics of ZnO MSM UV photodetector with Ni contact electrodes on poly propylene carbonate (PPC) plastic substrate

In this study, we report the fabrication of ZnO metal-semiconductor-metal UV photodetector (MSM UV PD) by deposition ZnO thin film on poly propylene carbonate (PPC) plastic substrate using direct current (DC) sputtering technique, and Nickel (Ni) contact as electrodes. The structural, optical and electrical properties of the ZnO thin film were investigated by using atomic force microscopy (AFM), X-Ray diffraction (XRD) measurement, and photoluminescence (PL). The electrical characteristics of the detector were investigated using the current–voltage (I–V) measurements, the dark- and photo-currents were found to be 1.04 and 93.80 μA, respectively. Using forward dark conditions at 5 volt; the barrier height Φ_B was calculated to be 0.675 eV. Under incident wavelength of 385 nm, it was found that the maximum responsivity (R) of the Ni/ZnO/Ni MSM PD was found to be 1.59 A/W.