Photoluminescence properties of Co-doped ZnO nanocrystals

We performed photoluminescence experiments on colloidal, Co²⁺-doped ZnO nanocrystals in order to study the electronic properties of Co²⁺ in a ZnO host. Room temperature measurements showed, next to the ZnO exciton and trap emission, an additional emission related to the Co²⁺ dopant. The spectral position and width of this emission does not depend on particle size or Co²⁺ concentration. At 8 K, a series of ZnO bulk phonon replicas appear on the Co²⁺-emission band. We conclude that Co²⁺ ions are strongly localized in the ZnO host, making the formation of a Co²⁺d-band unlikely. Magnetic measurements revealed a paramagnetic behaviour.     

Shape controllable synthesis of ZnO nanorod arrays via vapor phase growth

ZnO nanorod arrays with peculiar morphologies were synthesized on (111)-oriented Si substrate and glass via a vapor phase growth. The morphology of the individual nanorod can be flat-headed bottle-like, and needle-like, which depends on the deposition positions relative to the source materials in the presence of a controlling element Se. In addition, the arrays of all the three morphologies exhibit good alignment and high coverage. This fabrication technique can be also used to direct the controllable growth of other nanomaterials with similar morphologies.     

Helical nanostructures of SiOx synthesized through the heating of Co-coated substrates

This paper presents the use of the simple annealing technique at 1000 °C to produce the helical nanostructures of SiO_x. We have employed the Co-coated Si substrates, with Co layer and Si substrate utilized as catalyst and Si source, respectively. Beside the ordinary straight nanowires, the helical nanowires such as nanosprings and nanorings were observed. The product was an amorphous structure of SiO_x. We have discussed the possible growth mechanism. Photoluminescence spectrum of the SiO_x nanostructures showed a blue emission at 428 nm and a green emission at 534 nm, respectively.     

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.     

Growth of carbon nanofibers on aligned zinc oxide nanorods and their field emission properties

Carbon nanofibers were grown by electrodeposition technique onto aligned zinc oxide (ZnO) nanorods deposited by hybrid wet chemical route on glass substrates. X-ray diffraction traces indicated very strong peak for reflections from (0 0 2) planes of ZnO. The Raman spectra were dominated by the presence of G band at about 1597 cm⁻¹ corresponding to the E_2g tangential stretching mode of an ordered graphitic structure with sp² hybridization and a D band at about 1350 cm⁻¹ originating from disordered carbon. Fourier transformed infrared studies indicated the presence of a distinct characteristic absorption peak at ∼511 cm⁻¹ for Zn-O stretching mode. Photoluminescence spectra indicated band edge luminescence of ZnO at ∼3.146 eV along with a low intensity peak at ∼0.877 eV arising out of carbon nanofibers. Field emission properties of these films and their dependence on the CNF coverage on ZnO nanorods are reported here. The average field enhancement factor as determined from the slope of the FN plot was found to vary between 1 × 10³ and 3 × 10³. Both the values of turn-on field and threshold field for CNF/ZnO were lower than pure ZnO nanorods.     

Electronic and magnetic properties of basic nanosystems of early 3d transition metals (Sc,Ti, V,Cr, and Mn)

This detailed and systematic theoretical study on the behavior of basic low dimensional (one- and two-dimensional) systems of early 3d transition metals should serve as a guideline to experimentalists as well as to theoreticians. We find that, lowering of dimensionality is favorable for emergence of magnetic ordering in all the systems studied, except Ti monolayers (MLs). For Ti MLs, both nonmagnetic and ferromagnetic states are degenerate within the numerical limits. For such a case, the interactions with substrate would play a decisive role in the magnetic ordering of the atoms in the ML. The total energy calculations show that the nonmagnetic and ferromagnetic states are almost degenerate for Cr and V MLs too; however, anti-ferromagnetic ordering is favored in these. The ferromagnetic ordering in Sc linear chains and anti-ferromagnetic ordering in MLs of Mn and Cr are found to be favored by a relatively larger margin showing good stability. Some low dimensional systems, showing electrons with only one kind of spin available at Fermi energy, may be suitable for spintronics related applications. The linear chains of Cr and Mn, and MLs of Sc are likely to form stable magnetic nanosystems as these exhibit almost saturated magnetic moment per atom around the equilibrium separation. The magnetic moment strengthens considerably as one goes from two- to one-dimension. Our results are supported qualitatively by available experimental results and offer a good insight into these nanosystems.     

Synthesis and luminescence behavior of Eu-doped CaF2 nanoparticles

Luminescent Ca_1−xF_2+x:Eu_x nanoparticles were synthesized by a chemical co-precipitation method in an ethanol solution. The Ca_1−xF_2+x:Eu_x nanoparticles exhibit a sphere-like morphology with particle diameter of about 15-20 nm. With increasing concentration of Eu³⁺ ion the intensity of XRD diffraction peaks decreased significantly and full width at half-maximum of the peaks increased gradually, which indicated that more Eu³⁺ ions resulted in the increase of structural defects. The emission spectrum of Ca_1−xF_2+x:Eu_x nanoparticles consisted of a few narrow, sharp lines corresponding to Eu³⁺ ions. The luminescence intensity of Ca_1−xF_2+x:Eu_x nanoparticles increased with increasing concentration of Eu³⁺ ion and reached a maximum at approximately 15 mol%.     

Preparation and properties of ZnO nanostructures by electrochemical anodization method

ZnO thin films with diverse nanostructures, including nanodot, nanowire and nanoflower, have been fabricated on zinc foils by a simple and rapid electrochemical anodization method. The ZnO thin films reveal very strong visible emission that is ascribed to the transition between V_OZn_i and valence band. Under the dc or ac electric field, the electroinduced surface wettability conversion from the superhydrophobic to hydrophilic state was observed and the generation of surface defective sites on ZnO films under electric field was used to explain the transition mechanism. This work provides a simple and rapid method for synthesizing different ZnO nanostructures in large scale, and electric field can be used to modulate the wettability of ZnO nanostructures.     

Magnetic properties of large-area one-dimensional WO2 and MoO2 nanorods

Large-area one-dimensional (1D) monoclinic WO₂ and MoO₂ nanorods in the space group P2₁/c were synthesized by reactive thermal evaporation. The as-synthesized 1D WO₂ and MoO₂ nanorods become soft magnetic materials at 10 K, implying that structural or magnetic transitions occur. There are large differences in saturation magnetization, the coercive field, and remanence between the 1D WO₂ and MoO₂ nanorods, although both 1D nanorods have a similar shape.     

Three-photon upconversion luminescence phenomenon for the green levels in Er/Yb codoped cubic nanocrystalline yttria

In this paper, we observed that in Er³⁺/Yb³⁺ codoped nanocrystals (NC), with the decreasing particle size and the increasing Yb³⁺ concentration, the upconversion luminescence (UCL) of the red emissions of gradually increased, while the green emissions of gradually diminished under 980 nm diode laser excitation. In NC with lower Yb³⁺ concentration, both the red and green emissions result from a two-photon excitation. In NC with higher Yb³⁺ concentration, the red emissions result from a two-photon excitation, while the green emissions dominantly result from a three-photon excitation. A model was provided for explaining the above UCL phenomena.     

The Al-doping and post-annealing treatment effects on the structural and optical properties of ZnO:Al thin films deposited on Si substrate

Al-doped ZnO (ZnO:Al) thin films with different Al contents were deposited on Si substrates using the radio frequency reactive magnetron sputtering technique. X-ray diffraction (XRD) measurements showed that the crystallinity of the films was promoted by appropriate Al content (0.75 wt.%). Then the ZnO:Al film with Al content of 0.75 wt.% was annealed in vacuum at different temperatures. XRD patterns revealed that the residual compressive stress decreased at higher annealing temperatures. While the surface roughness of the ZnO:Al film annealed at 300 °C became smoother, those of the ZnO:Al films annealed at 600 and 750 °C became rougher. The photoluminescence (PL) measurements at room temperature revealed a violet, two blue and a green emission. The origin of these emissions was discussed and the mechanism of violet and blue emission of ZnO:Al thin films were suggested. We concluded that the defect centers are mainly ascribed to antisite oxygen and interstitial Zn in annealed (in vacuum) ZnO:Al films.     

Syntheses of nanocrystalline BaTiO3 and their optical properties

Stoichiometric and titanium-excess nanocrystalline barium titanates were synthesized using a hydrothermal process at various hydrothermal temperatures and with further heat treatment at 500 °C and 900 °C. Owing to the different process conditions, the excess titanium exists in different states and configurations within the nanocrystalline BaTiO₃ matrix; this was demonstrated by X-ray diffraction, Raman scattering, and photoluminescence. In these nanocrystalline BaTiO₃, the 590, 571, 543 and 694 nm light emission bands were observed; mechanisms leading to such emissions were also discussed. Received: 23 February 2001 / Accepted: 10 May 2001 / Published online: 27 June 2001     

Nonlinear optical properties of Au/ZnO nanoparticle arrays

The triangular-shaped Au/ZnO nanoparticle arrays were fabricated on fused quartz substrate using nanosphere lithography. The structural characterization of the Au/ZnO nanoparticle arrays was investigated by atomic force microscopy. The absorption peak due to the surface plasmon resonance of Au particles at the wavelength of about 570 nm was observed. The nonlinear optical properties of the nanoparticle arrays were measured using the z-scan method at a wavelength of 532 nm with pulse duration of 10 ns. The real and imaginary part of third-order nonlinear optical susceptibility, Re χ⁽³⁾ and Im χ⁽³⁾, were determined to be 1.15 × 10⁻⁶ and −5.36 × 10⁻⁷ esu, respectively. The results show that the Au/ZnO nanoparticle arrays have great potential for future optical devices.     

Synthesis and magnetic properties of CeVO3 nanostructures

CeVO₃ nanocrystals were fabricated by sintering CeVO₄ precursors in flowing hydrogen. Under an applied field of 20 Oe, a G-type orbital ordering transition, corresponding to the cooperative Jahn-Teller distortion, was enhanced and observed from the magnetization curve of CeVO₃ nanorods, different from that of the nanocrystallites. This enhancement of the orbital ordering transition depended on the giant magnetocrystalline anisotropy induced by strong crystallographic anisotropy. Furthermore, a stronger applied field decreased the anisotropy of electronic state induced by spatial shapes of orbitals and confined the cooperative Jahn-Teller distortion by lifting the orbital degeneracy, leading to the suppression of the orbital ordering transition.     

Rapid thermal annealing effects on the structural and optical properties of ZnO films deposited on Si substrates

The structural and optical properties of ZnO films deposited on Si substrate following rapid thermal annealing (RTA) have been investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL) measurements. After RTA treatment, the XRD spectra have shown an effective relaxation of the residual compressive stress, an increase of the intensity and narrowing of the full-width at half-maximum (FWHM) of the (0 0 2) diffraction peak of the as-grown ZnO film. AFM images show roughening of the film surface due to increase of grain size after RTA. The PL spectrum reveals a significant improvement in the UV luminescence of ZnO films following RTA at 800 °C for 1 min.     

Influence of Al-doping on the structure and optical properties of ZnO films

Al-doped ZnO (ZnO:Al) thin films with c-axis preferred orientation were deposited on glass substrates using the radio frequency reactive magnetron sputtering technique. The effect of Al concentrations on the microstructure and the luminescence properties of the ZnO:Al thin films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), and fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted by appropriate Al concentrations; the photoluminescence spectra (PL) of the samples were measured at room temperature. Strong blue peak located at 437 nm (2.84 eV) and two weak green peaks located at about 492 nm (2.53 eV) and 524 nm (2.37 eV) were observed from the PL spectra of the four samples. The origin of these emissions was discussed. In addition, absorption and transmittance properties of the samples were researched by UV spectrophotometer; the UV absorption edge shifted to a shorter wavelength first as Al was incorporated, and then to a longer wavelength with the increasing Al concentrations. The optical band gaps calculated based on the quantum confinement model are in good agreement with the experimental values.     

Photoluminescence properties of nitrogen-doped ZnO films deposited on ZnO single crystal substrates by the plasma-assisted reactive evaporation method

Photoluminescence (PL) spectra of nitrogen-doped ZnO films (ZnO:N films) grown epitaxially on n-type ZnO single crystal substrates by using the plasma-assisted reactive evaporation method were measured at 5 K. In PL spectra, free exciton emission at about 3.375 eV was very strong and emissions at 3.334 and 3.31 eV were observed. These two emissions are discussed in this paper. The nitrogen concentration in ZnO:N films measured by secondary ion mass spectroscopy was 10^19-20 cm⁻³. Current-voltage characteristics of the junction consisting of an n-type ZnO single crystal substrate and ZnO:N film showed good rectification. Also, ultraviolet radiation and visible light were emitted from this junction under a forward bias at room temperature. It is therefore thought that ZnO:N films have good crystallinity and that doped nitrogen atoms play a role as acceptors in ZnO:N films to form a good pn junction. From these phenomena and the excitation intensity dependency of PL spectra, emissions at 3.334 and 3.31 eV were assigned to neutral acceptor-bound exciton (A⁰X) emission and a donor-acceptor pair (DAP) emission due to doped nitrogen, respectively.     

The structural and optical properties of ZnO nanorod arrays

High quality vertical-aligned ZnO nanorod arrays were synthesized by a simple vapor transport process on Si (111) substrate at a low temperature of 520 °C. Field-emission scanning electron microscopy (FESEM) showed the nanorods have a uniform length of about 1 μm with diameters of 40-120 nm. X-ray diffraction (XRD) analysis confirmed that the nanorods are c-axis orientated. Selected area electron diffraction (SAED) analysis demonstrated the individual nanorod is single crystal. Photoluminescence (PL) measurements were adopted to analyze the optical properties of the nanorods both a strong UV emission and a weak deep-level emission were observed. The optical properties of the samples were also tested after annealing in oxygen atmosphere under different temperatures, deep-level related emission was found disappeared at 600 °C. The dependence of the optical properties on the annealing temperatures was also discussed.     

Effect of surface preparation on the morphology of ZnO nanorods

The effects of Si substrate orientation and surface treatment on the morphology and density of Zinc oxide (ZnO) nanorods were investigated. The size and density of ZnO nanorods were influenced by Si substrate orientation and surface preparation. ZnO nanorods synthesized on the ideally H-terminated Si(1 1 1) prepared with an NH₄F solution resulted in the biggest size and the lowest density. It is suggested that the smoother surface of the Si substrate and lattice shape match with a larger atomic distance result in the increase of the ZnO seedlayer's grain size, which in turn enhances the size of ZnO nanorods grown on it. The optical properties of the ZnO nanorods were affected by their size and crystallinity. The smallest ZnO nanorods with a preferential c-axis orientation synthesized on the HF-treated Si(1 1 1) surface showed the highest intensity ratio of UV to visible emission, and the biggest ZnO nanorods synthesized on the N₂-sparged NH₄F-treated Si(1 1 1) surface showed the lowest intensity ratio of UV to visible emission. Therefore, it can be concluded that Si substrate orientation and surface preparation significantly affect the optical properties of ZnO nanorods.     

Photoluminescence and time-resolved photoluminescence of star-shaped ZnO nanostructures

Optical properties of star-shaped ZnO nanostructures were studied. The temperature-dependent photoluminescence (PL) was examined up to fourth-order longitudinal optical (LO) phonon assisted emissions of free excitons and confirmed that the nature of the room temperature PL in ZnO is 1-LO phonon assisted emission of free excitons. Low threshold ultraviolet stimulated emissions (SE) were obtained for our powder samples at room temperature. Picosecond time-resolved PL measurements detected a bi-exponential decay behavior which is strongly dependent on the excitation intensity: the slow decay term decreased faster than the fast decay term as the excitation intensity increased and the emission decays were dominated by the fast one. We also found that the emission decays decreased super-linearly before the appearance of the SE. This behavior may be used to deduce the threshold of SE or lasing.