Decay dynamics of ultraviolet photoluminescence in ZnO nanocrystals

Time resolved photoluminescence (PL) measurements at low temperature are performed on colloidal ZnO nanocrystals dispersed in t-butanol. Considering the particle size dependence of the decay times we conclude that the luminescence is composed of two trap related emissions one of which undergoes lifetime shortening due to a non-radiative process. Initial fast shift of the spectrum within 30 ps is observed and it is interpreted as a fast hole cooling just after the excitation.     

Temperature induced size selective synthesis of hybrid Cds/pepsin nanocrystals and their photoluminescence investigation

There is growing interest in materials chemistry for taking advantage of the physical and chemical properties of biomolecules in the development of next generation nanoscale materials for opto-electronic applications. A biomimetic approach to materials synthesis offers the possibility of controlling size, shape, crystal structure, orientation, and organization. The great progress has been made in the control that can be exerted over optical materials synthesis using biomolecules (protein, nucleic acid)/mineral interfaces as templates for directed synthesis. We have synthesized the CdS nanocrystals using pepsin by biomimetic technique at four different set temperatures. X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) results showed that we are able to tune the size and distribution profile just by tuning the reaction (Rx) temperature and goes towards excitonic Bhor radius (2.5 nm) at low temperature (4 °C). The narrow absorption peak at 260 nm from Cd²⁺-pepsin complex dominates and indicates the size dispersion of the modified CdS nanoparticles are fairly monodisperse. Effective mass approximation (EMA) shows large blue-shift (~1 eV) in the band gap for the cubic phase from bulk hexagonal CdS. The photoluminescence (PL) and photoluminescence excitation (PLE) spectra are dominated by a strong and narrow band-edge emission tunable in the blue region indicating a narrow size distribution. The reduction in PL efficiency is observed when the Rx temperature increases however no change in PLE spectra and temporal profiles of the band-edge PL is observed. At 4 °C, high emission efficiency with shift of PL spectrum in the violet region is observed for 1.7 nm size CdS quantum dots (QDs). Presence of pepsin has slowed the PL decay which is of the order of 100 μs.     

Synthesis of ZnO nanowires by pulsed laser deposition in furnace

ZnO nanowires were fabricated on Au coated (0 0 0 1) sapphire substrates by using a pulsed Nd:YAG laser with a ZnO target in furnace. ZnO nanowires have various sizes and shapes with a different substrate position inside a furnace. The length and the diameter of these ZnO nanowires were around 3-4 μm and 120-200 nm, respectively, confirmed by scanning electron microscopy (SEM). The diameter control of the nanowires was achieved by varying the position of substrates. The ultraviolet emission of nanowires from the near band-edge emission (NBE) was observed at room temperature. The formation mechanism and the effect of different position of substrates on the structural and optical properties of ZnO nanowires are discussed.     

Controlled synthesis and phase characterization of Fe-based nanoparticles obtained by thermal decomposition

Iron oxide nanoparticles were synthesized by the thermal decomposition of Fe(acac)₃ and Fe(CO)₅. Three different homogeneous procedures were used for the controlled synthesis of Fe₃O₄, γ-Fe₂O₃ and Fe₃O₄/γ-Fe₂O₃ mixture nanocrystals. A combination of characterization techniques was used in order to distinguish these oxides. The controllable size, the narrow distribution and the rhombic self-assembly of the nanoparticles were revealed by the high-resolution transmission electron microscopy images and the X-ray powder diffraction results. For the quantitative analysis of the samples manganometry was used. Preliminary magnetic measurements indicated the size and composition dependence of saturation magnetization, a superparamagnetic behavior of the samples and some ferromagnetic features.     

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.     

Sol-gel synthesis of sub-50 nm ZnO nanowires on pulse laser deposited ZnO thin films

A simple synthesis route to high-quality sub-50 nm ZnO nanowires is reported, utilizing ZnO thin films grown by pulse laser deposition (PLD) as seed layers. Depending upon the PLD growth conditions, the surface morphology of the ZnO nanowires on ZnO film was distinctively different whereas the diameters were almost the same. With the increase of the concentration of zinc nitrate/methenamine solution from 0.002 to 0.02 M, the average diameter of the ZnO nanowire increased but remained sub-50 nm. The grown ZnO nanowires showed a high crystallinity with a low defect density confirmed by a sharp photoluminescence spectrum.     

Interphase synthesis and some characteristics of aqueous nickel dispersions

The facilities of one-step preparation method of nickel nanoparticles by the interphase reduction of nickel oleate using sodium borohydride at room temperature without soluble polymer as a protective agent were studied. Nickel obtained by such technique was concentrated in aqueous phase as a black dispersion. The composition and morphology of the colloid's dispersive phase were investigated by transmission electron microscopy, XRD and IR-spectroscopy. The dispersive phase of the prepared colloidal solution represents crystalline spherical nickel nanoparticles with some admixture of nickel boride. Their average size varies between 2 and 6 nm. In accordance with the IR-spectroscopy results the stability of the nickel colloidal dispersions was provided by the surfactant produced through the interphase reaction.     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

Cobalt nanoparticles synthesis from Co(CH3COO)2 by thermal decomposition

Nontoxic cobalt acetate tetrahydrate was used as a precursor to prepare cobalt nanoparticles of 8–200 nm in average diameter by thermal decomposition. The different combinations of trioctylphosphine, oleylamine and oleic acid were added as surfactants to control the particle size. These combinations resulted in the particles with saturation magnetization and coercive force ranging from 55.0 to 100.1 emu/g and from 0 to 459.3 Oe, respectively.     

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.     

Study of the morphological evolution of ZnO nanostructures on various sapphire substrates

Zinc oxide (ZnO) nanostructures were grown on A-, C- and R-plane sapphires by metal organic chemical vapor deposition (MOCVD) technique. The shape of nanostructures was greatly influenced by the underlying sapphire substrate. Vertical aligned nanowires were observed on A- and C-plane sapphires, whereas the nanopencils were grown on R-plane sapphire. A correlation between the morphological and optical properties of the nanostructures has been established, where the morphological and structural characteristics are responsible for the evolution of optical properties. The nanowires, grown on C-plane sapphires, have shown superior optical properties. Comparatively higher photo-induced wettability transition has also been observed for ZnO nanostructures on R-plane sapphire.     

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.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Patterned aluminum nanowires produced by electron beam at the surfaces of AlF3 single crystals

Cubic- and rectangular-shape single crystals of α-AlF₃ in sizes of 5-50 μm have been synthesized by a solid-vapor phase process. Using the electron beam induced decomposition of AlF₃, a method is demonstrated for fabricating patterned aluminum nanowires in AlF₃ substrate in a scanning electron microscope. By controlling the accelerating voltage, the beam current and scanning time, it is possible to fabricate metallic nanowires of different sizes. The aluminum nanowires may act as nano-interconnects for nanoelectronics. This work demonstrates a potential technique for e-beam nanofabrication.     

Details of crystalline growth in co-deposited electroplated nickel films with hard (nano)particles

Electroplated nickel dispersion films with incorporated hard particles, primarily titanium oxide, were studied. A sufficient dispersion of nanometre-scaled particles in Watts solution was reached by application of ultrasonic energy to the galvanic bath. Crystal morphology, mean grain size and formation of textures were examined by electron backscattering diffraction (EBSD), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The typical columnar structure of pure Ni films was refined by means of ultrasound. Incorporation of micron-sized TiO₂ particles generates additional nucleation surfaces in contrast to SiC particles. Textures of the subsequent columnar nickel crystals change from 〈2 1 1〉 (silent condition) or 〈1 1 0〉 (ultrasonic condition) fibre textures in growth direction to 〈1 0 0〉 and 〈1 1 1〉 textures under the influence of nanoparticle incorporation. Moreover, nanoparticles remarkably decrease the grain size and grain aspect ratio. Their incorporation takes place inside the crystals as well as between grains.     

Cr-doping induced ferromagnetic behavior in antiferromagnetic EuTiO3 nanoparticles

We have synthesized a series of high quality EuTi_1−xCr_xO₃ (x = 0.0, 0.02, and 0.04) nanoparticles by simple sol-gel technique. The averaged grain size of these obtained nanoparticles displays no obvious change with Cr-doping and is about 100 nm. The structural and magnetic properties of EuTi_1−xCr_xO₃ (x = 0.0, 0.02, and 0.04) samples were detailedly investigated. It is found that the G-antiferromagnetic (G-AFM) ordering of pure EuTiO₃ can be significantly modified with slight Cr-doping, and finally the ferromagnetic behavior is enhanced for EuTi_1−xCr_xO₃ system with Cr-doping.     

Nonlinear optical properties of periodic gold nanoparticle arrays

Periodic Au nanoparticle arrays were fabricated on silica substrates using nanosphere lithography. The identical single-layer masks were prepared by self-assembly of polystyrene nanospheres with radius R = 350 nm. The structural characterization of nanosphere masks and periodic particle arrays was investigated by atomic force microscopy. The nonlinear optical properties of the Au nanoparticle arrays were determined using a single beam z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that periodic Au nanoparticle arrays exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 6.09 × 10⁻⁶ cm²/kW and β = −1.87 × 10⁻⁶ m/W, respectively.     

Fabrication of highly ordered and stepped ZnO comb-like structures

Highly ordered and stepped ZnO comb-like structures were fabricated using conventional thermal evaporation method. Zn powder covered by a layer of a mixture of ZnO and graphite was employed as the Zn source. The obtained ZnO comb-like structures are several tens of micrometers and some of them are even up to 100 μm. Both the widths of the belts and the lengths of the branches gradually decrease along the growth direction of ZnO comb-like structures. Under the most suitable condition, ZnO nanorods branches have uniform diameters and are evenly distributed on the belt-like stem. Possible growth process of ZnO comb-like structures was discussed. The effect of growth temperature on the morphology of the obtained products was also investigated. Room-temperature photoluminescence spectra from the ZnO comb-like structures and the nanorods film reveal weak UV emission and strong green emission.     

Aligned growth of ZnO nanowires by NAPLD and their optical characterizations

Not only vertically aligned ZnO nanowires but also horizontally aligned ZnO nanowires have been successfully grown on the annealed (0 0 0 1) c-cut and (1 1 2 0) a-cut sapphire substrates, respectively using catalyst-free nanoparticle-assisted pulsed-laser ablation deposition (NAPLD). The as-synthesized ZnO nanowires exhibit an ultraviolet emission at around 390 nm and the absent green emission under room temperature. The single ZnO nanowire was collected in the electrode gap by dielectrophoresis (DEP). Under the optical pumping, the single ZnO nanowire exhibited UV emission at around 390 nm with several sharp peaks whose energy spacings are almost constant, which greatly differs from the broad UV emission of the film with many nanowires, suggesting ZnO nanowires as candidates for laser media. The single ZnO nanowire showed polarized photoluminescence (PL). The as-synthesized ZnO nanowires could find many interesting applications in short-wavelength light-emitting diode (LED), laser diode and gas sensor.     

Influence of the local absorber layer thickness on the performance of ZnO nanorod solar cells

The local absorber layer thickness (d_local) of solar cells with extremely thin absorber was changed between 10 nm and 70 nm. As a model system, ZnO nanorod arrays (electron conductor) with fixed internal surface area coated with In₂S₃ (absorber) and impregnated with CuSCN (transparent hole conductor) were applied. The performance of the small area solar cells depended critically on d_local. The highest short circuit current density was reached for the lowest d_local. In contrast, the highest open circuit voltage was obtained for the highest d_local. A maximum energy conversion efficiency of 3.4% at AM1.5 was achieved. Limiting factors are discussed.(© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)