Defect-related Green Emission Research Articles

Catalyst-free synthesis of honeycomb-like and straight ZnO nanowires

Honeycomb-like ZnO nanowire arrays and straight nanowires were directly grown on the carbon-coated Si substrates without the aid of any metal catalysts, revealing an interesting growth behavior. It is found that one-dimensional (1D) nanostructures can easily grow on the carbon surface at different temperature region mainly due to the large difference in interface energy between the ZnO and C surface. Both the honeycomb-like nanowire arrays and straight nanowires exhibit excellent ultraviolet (UV) quality and common defect-related green emissions are almost not detected, indicating their perfect crystalline nature.

Depth-resolved cathodoluminescence study of zinc oxide nanorods catalytically grown on p-type 4H-SiC

Optical properties of ZnO nanorods (NRs) grown by vapour–liquid–solid (VLS) technique on 4H-p-SiC substrates were probed by cathodoluminescence (CL) measurements at room temperature and at 5 K complemented with electroluminescence. At room temperature the CL spectra for defect related emission intensity was enhanced with the electron beam penetration depth. We observed a variation in defect related green emission along the nanorod axis. This indicates a relatively poor structural quality near the interface between ZnO NRs and p-SiC substrate. We associate the green emission with oxygen vacancies. Analysis of the low-temperature (5 K) emission spectra in the UV region suggests that the synthesized nanorods contain shallow donors and acceptors.

Structural, optical and magnetic characterization of Cu-doped ZnO nanoparticles synthesized using solid state reaction method

Polycrystalline undoped and Cu-doped Zinc oxide (Zn0.98Cu0.02O) nanocrystals were successfully synthesized by solid-state reaction method. The micro structural, optical and magnetic properties have been characterized using powder X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive analysis using X-rays (EDAX), UV–Visible spectroscopy, Photoluminescence, Vibrating sample magnetometer and Electron paramagnetic resonance spectroscopy. XRD pattern reveals that the samples possess hexagonal wurtzite structure of ZnO without any secondary phase after copper doping. Optical absorption analysis of the samples showed a red shift in absorption band edge with copper doping in ZnO. Photoluminescence spectra of the samples shows prominent peaks corresponding to near band edge UV emission and defect related green emission in the visible region at room temperature and their possible mechanism have also been discussed. Magnetic measurements using VSM showed that the nanocrystalline copper doped ZnO exhibits ferromagnetic behaviour at 300 K. EPR analysis also confirms the substitution of Zn site by Cu2+.

Structure and optical properties of nanostructured zinc oxide films with different growth temperatures

ZnO films were prepared by pulsed laser deposition (PLD) on glass substrate with temperature ranging from room temperature (RT) to 500 °C. All the films formed the hexagonal wurtzite structure and showed the c-axis (0 0 2) preferred orientation. The films deposited at 200 °C showed the narrowest full width at half maximum of both X-ray diffraction (XRD) and rocking curve, largest height grain size, smallest macrostress and least point defects. Meanwhile, it was found that the films deposited at 350 °C displayed the most intense diffraction peak in XRD and a strong UV emission while it showed the most intense defect-related green emission, fastest growth rate and larger macrostress. In addition, the cross section images showed all films grew with a columnar form along (0 0 2) orientation.

Nanostructured surface morphology of ZnO grown on p-type GaN and Si by metal organic chemical vapor deposition

The surface morphology of ZnO grown on p-GaN templates and p-Si (1 1 1) substrates at various temperatures by metal organic chemical vapor deposition (MOCVD) in a vertical reactor at atmospheric pressure is reported. A low temperature ZnO buffer was deposited initially at 200 °C for 15 min as a nucleation layer. Epitaxial ZnO was grown at 500 °C, 550 °C, 600 °C for 40 min, respectively. Uniformly distributed and well-aligned ZnO nanorods with diameter in the range 80–120 nm and length ∼0.7 μm were observed for deposition on p-GaN template. By contrast, the morphology of ZnO epilayers grown on p-Si (1 1 1) transitioned from 2D to 3D with increasing growth temperature. X-ray diffraction (XRD) spectra showed all the ZnO epilayers had the hexagonal wurtzite structure but different preferred orientation. PL spectra showed only free-exciton emission at 378 nm (∼3.28 eV) with a full width at half maximum of 13 nm without defect-related green emission in the epitaxial ZnO grown at 550 °C and 600 °C. The epitaxial ZnO layers grown on p-GaN and p-Si at the same temperature have similar PL spectra. The PL measurement also exhibits strong exciton-related emission without defect peak, which showed that the ZnO nanostructures grown at 550 °C and 600 °C have good optical properties with excellent crystal quality.

Luminescent properties of ZnO nanowires and as-grown ensembles

Vertically aligned ZnO nanowires were synthesized on a sapphire () substrate by vapour deposition and their light-emitting properties were characterizedusing photoluminescence and cathodoluminescence spectroscopies. Besides the nanowires,there exists a mosaic ZnO film on the substrate surface. Comparison of the luminescentproperties of the as-grown ensemble and the nanowires extracted from it shows that themosaic film is the major source of the defect-related green emission while the nanowirespossess highly crystalline quality with virtually no defects. Photoemission spectroscopyshows that the valence band states associated with O 2p from the as-grown sample arediminished compared with those from the extracted nanowires. These findings suggest thatthe green emission partly arises from oxygen vacancies located on the surface of the mosaicfilm.

Morphology-controlled synthesis, growth mechanism, optical and microwave absorption properties of ZnO nanocombs

ZnO nanocombs and nanorods with different morphologies have been successfully synthesized through a simple metal vapour deposition route at 600–750 °C using pure zinc powder or zinc and graphite powders as source materials. The structures and morphologies of the products were characterized in detail by using x-ray diffraction, scanning electron microscopy, transmission electron microscopy and laser Raman spectrometer. The morphologies of the products can be easily controlled by tuning the following four factors: reaction temperature, the distance between the source and the substrates, the kinds of substrates and the kinds of precursors. Possible growth mechanisms for the formation of ZnO nanostructures with different morphologies are discussed. Photoluminescence studies show that there are sharp UV and broad defect-related green emissions for all products. Relative intensity of the UV to defect-related green emissions decreases from ZnO nanorods to nanocombs. Microwave absorption properties of these nanocombs are also investigated. The value of the minimum reflection loss is −12 dB at 11 GHz for the ZnO nanocomb composite with a thickness of 2.5 mm.

Enhanced optical and field emission properties of CTAB-assisted hydrothermal grown ZnO nanorods

We have developed a simple N-cetyl- N, N, N-trimethyl ammonium bromide (CTAB)-assisted hydrothermal route for the production of ZnO one-dimensional (1D) nanostructures on zinc foil at reaction temperature of 160 °C. With the increase of CTAB concentration, the one-dimensional structures change from microrod to a mixture of nano- and microrod and finally to nanorods. X-ray diffraction studies confirmed the proper phase formation of the grown nanostructures. The room temperature photoluminescence spectra showed that ZnO nanostructures prepared with increased CTAB concentration exhibited enhanced band edge UV emission and also blue shift of the emission peak. All the samples show no defect related green emission. Field emission property of the 1D structures has been investigated in detail. By tuning the CTAB concentration, the field emission property was optimized. The nanorods synthesized with high CTAB showed turn-on and threshold fields of 3.2 and 5 V/μm, respectively, which are comparable to the values for vapour phase synthesized high field emitting ZnO nanostructures.

Microphotoluminescence study of individual suspended ZnO nanowires

We report microphotoluminescence measurements on individually suspended ZnO nanowires attached to nanometer-sized metal tips. This procedure avoids the possible influence of the substrate and enables comprehensive optical, electrical, chemical, and morphological characterizations to be carried on the same individual nanowire. Based on the ZnO nanowires examined, we found that the near band edge emission redshifted with the increasing intensity of the defect-related green emission. The comprehensive characterizations of in situ heated ZnO nanowires suggested a correlation between the defect green emission and the oxygen deficiency, which also affect the carrier density, and thus, the nanowire’s transport property.

Optical properties of zinc oxide nanocrystals embedded in mesoporous silica

This paper reports on the synthesis and characterization of a nanocomposite incorporating zinc oxide (ZnO) in mesoporous silica (MPS), a host medium for stabilizing the nanoparticles. The composite is prepared using a chemical route involving in-situ synthesis of ZnO in pores of host material in an acidic medium. The samples are characterized by X-ray Diffraction (XRD), Energy Dispersive Spectroscopy (EDS), high resolution Transmission Electron Microscopy (TEM), UV–Vis absorption and Photoluminescent (PL) spectroscopy. The UV–Vis spectra and the PL spectra of the composite show blue shift in the position of the absorption band, indicating quantum confinement effect. On excitation at 320 nm, the samples exhibit a relatively narrow UV fluorescence emission band around 350 nm and an exciton recombination luminescence peak around 405 nm. The generally observed defect-related green emission is not observed, possibly being too low in intensity when compared to UV/blue emission.

ZnO nanocones: Solvothermal synthesis and photoluminescence properties

Ellipsoidal and prism shaped ZnO nanocrystals with hexagonal cross-sections have been synthesized by a simple solvothermal process. The ellipsoidal ZnO nanocrystals possessed a unique hexagonal cross-section having two sharp pointed ends and a flattened central part. The well faceted prism like particles resembled hexagonal cones in their shape. Dimensions of the nanocrystals increased systematically with the increase in the synthesis temperature. The synthesized nanocrystals exhibited near band edge UV emission centered at ∼400 nm. An additional defect related green emission band at ∼500 nm was observed from the samples synthesized at higher temperatures.

Origin of defect-related green emission from ZnO nanoparticles: effect of surface modification

We investigated the optical properties of colloidal-synthesized ZnO spherical nanoparticles prepared from 1-octadecene (OD), a mixture of trioctylamine (TOA) and OD (1:10), and a mixture of trioctylphosphine oxide (TOPO) and OD (1:12). It is found that the green photoluminescence (PL) of samples from the mixture of TOA/OD and TOPO/OD is largely suppressed compared with that from pure OD. Moreover, it is found that all spherical nanoparticles have positive zeta potential, and spherical nanoparticles from TOA/OD and TOPO/OD have a smaller zeta potential than those from OD. A plausible explanation is that oxygen vacancies, presumably located near the surface, contribute to the green PL, and the introduction of TOA and TOPO will reduce the density of oxygen vacancies near the surfaces. Assuming that the green emission arises due to radiative recombination between deep levels formed by oxygen vacancies and free holes, we estimate the size of optically active spherical nanoparticles from the spectral energy of the green luminescence. The results are in good agreement with results from TEM. Since this method is independent of the degree of confinement, it has a great advantage in providing a simple and practical way to estimate the size of spherical nanoparticles of any size. We would like to point out that this method is only applicable for samples with a small size distribution.

Photoluminescence of ZnO layer on commercial glass substrate prepared by sol–gel process

Amorphous ZnO thin film on soda–lime–silica glass substrate was prepared by the sol–gel process at low-temperature processing, i.e., 100 °C. No distinct grain structure was observable in the surface of the film. The photoluminescence spectrum of the ZnO thin film with an intense near band edge emission was observed while the defect-related broad green emission was nearly quenched.

Simple Solvothermal Route To Synthesize ZnO Nanosheets, Nanonails, and Well-Aligned Nanorod Arrays

ZnO nanosheets, nanonails, and well-aligned nanorods were fabricated on Zn foils by a solvothermal approach using ethanol as the solvent. A lower synthesis temperature and a shorter time period favor the formation of nanosheets. By optimizing the synthesis temperature and time period, ZnO nanonails with a hexagonal cap and a long stem could be produced. A higher temperature was not favorable to produce uniform and smooth nanorods. Well-aligned ZnO nanorod arrays were produced with diameters within 100-250 nm and lengths up to approximately 6 microm when NaOH was added to the solvent. By optimizing the reaction parameters, the morphology, size, and orientation of the nanoforms could be tailored. The ZnO nanorods exhibit an excitonic strong UV emission and a defect-related broad green emission at room temperature. The defect-related green emission band decreased with the improvement of the degree of alignment of the nanorods.

Temperature and pressure dependences of the copper-related green emission in ZnO microrods

We have investigated the temperature and pressure dependences of the copper-related green emission, which show fine structure at low temperature, from tetrapodlike ZnO microrods. The temperature dependence of the green emission energy follows the changes in the band gap from 10–200K, but deviates from this behavior above 200K. The pressure dependence of the copper-related green band (25±5meV∕GPa) is similar to that of the band gap of ZnO, and is larger than that reported previously for defect-related green emission in ZnO.

Morphology evolution and photoluminescence properties of ZnO films electrochemically deposited on conductive glass substrates

The current-dependent morphology evolution and photoluminescence properties of zinc oxide (ZnO) films prepared by electrochemical deposition (ECD) method were studied in this paper. It has been shown that the morphologies of ZnO films vary from porous to dense structure, from pillar crystal array to two-dimensional nanosheet covered film, with increase of deposition currents. Correspondingly, orientation of the film evolves from randomly to highly c-axis oriented structure. Current dependence of morphology is attributed to the ECD current-controlled preferential growth velocity along the c axis. All the ZnO films prepared over a wide current range show strong ultraviolet (UV) emission at room temperature, which also shows deposition current dependence in intensity, together with relatively weak defect-related green emission under UV excitations. Further experiments have revealed that a nonradiative relax process and a radiative electron-hole combination process are involved in this defect-related green emission and the excitonic origin of UV emission was also proved.

Morphology-Controlled Synthesis of ZnO Nanostructures by a Simple Round-to-Round Metal Vapor Deposition Route

One-dimensional ZnO nanostructures with different morphologies have been successfully synthesized through a simple round-to-round metal vapor deposition route at 550 degrees C with a zinc powder covered indium film as the source material. The structures and morphologies of the products were characterized in detail by using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Studies found that the morphology of the products can be easily tuned from one experimental round to another. Possible growth mechanisms for the formation of one-dimensional ZnO nanostructures with different morphologies are discussed. Photoluminescence studies show that there are sharp UV emission and broad defect-related green emissions for the products obtained in all experimental rounds. Relative intensity of the UV emission to defect-related emissions gradually increased from one experimental round to another.

Highly monodisperse polymer-capped ZnO nanoparticles: Preparation and optical properties

We report the preparation of highly monodisperse ZnO nanoparticles using poly(vinyl pyrrolidone) (PVP) as the capping molecules. The surface-modified ZnO nanoparticles were found to be remarkably stable. The optical absorption shows distinct excitonic features. Markedly enhanced near-band-edge ultraviolet photoluminescence and significantly reduced defect-related green emission were also observed. We attribute this observation to the nearly perfect surface passivation of the ZnO nanoparticles by the PVP molecules. The third-order nonlinear optical response of these PVP-capped ZnO nanoparticles in a dilute solution was found to be significantly larger (by at least two orders of magnitude) than that of the bulk ZnO.