Catalytic and non-catalytic growth of amorphous silica nanowires and their photoluminescence properties

A simple method based on the thermal oxidation of Si wafers in presence of a mixture of MgO and graphite powder was developed for large-scale synthesis of very long amorphous silica nanowires. The synthesis was done with and without gold as the catalyst. Almost aligned uniform nanowires with diameters within 60-90 nm and length up to few hundred micrometers were obtained using gold as the catalyst while bicycle chain like nanowires were obtained in absence of the catalyst. The growth sequence of the nanowires was observed through scanning electron microscope. Both forms of the nanowires emitted blue lights at 414 nm (3 eV) under excitation at 250 nm.     

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.     

Luminescence of ZnO nanocrystals capped with an organic dye

ZnO nanocrystals capped with an organic dye Rhodamine 6G (Rh6G) were investigated by photoluminescence (PL) and cathodoluminescence (CL) techniques. PL and CL spectra showed a remarkable decrease in visible emission intensity after ZnO nanocrystals were capped with Rh6G, indicating that dangling bonds and defect states existing at the surface of ZnO nanocrystals were significantly passivated. Rh6G on the ZnO surface exhibited a monomer-like emission, and the intensity and the position of the emission were dependent on the dye concentration.     

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%.     

Evidence for fast decay dynamics of the photoluminescence from Ge nanocrystals embedded in SiO2

We have investigated the origin of room temperature photoluminescence from ion-beam synthesized Ge nanocrystals (NCs) embedded in SiO₂ using steady state and time-resolved photoluminescence (PL) measurements. Ge NCs of diameter 4-13 nm were grown embedded in a thermally grown SiO₂ layer by Ge⁺ ion implantation and subsequent annealing. Steady state PL spectra show a peak at ∼2.1 eV originating from Ge NCs and another peak at ∼2.3 eV arising from ion-beam induced defects in the SiO₂ matrix. Time-resolved PL studies reveal double exponential decay dynamics on the nanoseconds time scale. The faster component of the decay with a time constant τ₁∼3.1 ns is attributed to the nonradiative lifetime, since the time constant reduces with increasing defect density. The slower component with time constant τ₂∼10 ns is attributed to radiative recombination at the Ge NCs. Our results are in close agreement with the theoretically predicted radiative lifetime for small Ge NCs.     

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.     

Photoluminescence in anatase titanium dioxide nanocrystals

Titanium dioxide (TiO₂) nanocrystals were prepared by a hydrolysis process of tetrabutyl titanate. X-ray diffraction and Raman scattering showed that the as-prepared TiO₂ nanocrystals have anatase structure of TiO₂, and that the monophase anatase nanocrystals can be achieved through a series of annealing treatments below 650 °C. We measured photoluminescence (PL) spectra of the TiO₂ nanocrystals. Under 2.41–2.71 eV laser irradiation, the TiO₂ nanocrystals displayed strong visible light emission with maxima of 2.15–2.29 eV even at excitation power as low as 0.06 W/cm². To identify the PL mechanism in the TiO₂ nanocrystals, the dependences of the PL intensity on excitation power and irradiation time were investigated. The experimental results indicated that the radiative recombination is mediated by localized levels related to surface defects residing in TiO₂ nanocrystallites. Received: 7 April 1999 / Revised version: 23 August 1999 / Published online: 30 November 1999     

Synthesis and photoluminescence of aligned straight silica nanowires on Si substrate

Aligned straight silica nanowires (NWs) have been synthesized on Si wafer by thermal evaporation of mixed powders of zinc carbonate hydroxide and graphite at 1100 °C and condensation on Si substrate without using any catalyst. The straight silica NWs have diameters ranging from 50 to 100 nm, and lengths of several micrometers, with cone-shaped tips at their ends. High deposition temperature and relatively high SiO_x vapor concentration near the growth substrate would be beneficial to the formation of the aligned straight silica NWs. Different morphologies of silica nanostructures have also been obtained by varying the deposition temperature and the vapor concentration of the SiO_x molecules. Room temperature photoluminescence measurements on the oriented silica NWs show that two green emission bands at 510 and 560 nm, respectively, revealing that the aligned straight silica NWs might have potential applications in the future optoelectronic devices.     

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.     

Influence of hydrogenation on the structure and visible photoluminescence of germanium oxide thin films

Substoichiometric germanium oxide thin films were prepared by evaporation of GeO₂ powder. The as-deposited samples showed a luminescence band in the visible range. Hydrogen was used to passivate the dangling bond defects and therefore to determine the origin of photoluminescence in the germanium oxide films. Hydrogen was introduced in the films from an electron cyclotron resonance (ECR) plasma source during or after the evaporation. The films hydrogenated during evaporation contain little oxygen because of an etching mechanism. In the post-hydrogenated films, the oxygen content is higher. With the hydrogenation treatment, the oxygen dangling bonds are suppressed. It is proposed that the photoluminescence in the visible range is attributed to the structural defects.     

Photoluminescence studies from silicon nanocrystals embedded in spin on glass thin films

Photoluminescence (PL) from silicon nanocrystals (Si-nc) prepared from pulverised porous silicon and embedded in undoped (SOG) or phosphorus-doped spin-on-glass (SOD) solutions was studied. Effects of rapid thermal annealing on the PL was also investigated. A strong room temperature PL signal was observed at 710 nm due to the recombination of electron-hole pairs in Si-nc and the PL maximum shifts to the blue region as the phosphorus concentration in the spin on glass increases. However, the rapid thermal annealing process (30 s, 900°C) quenches the PL response. These results suggest that for Si-nc/SOG (SOD) the surface termination is efficient but high phosphorus doping of Si-nc is detrimental to the PL.     

Microstructure and multiphoton luminescence of Au nanocrystals prepared by using glancing deposition method

Au crystal columns embedded in SiO₂ with an average length of 480 nm and diameter of 30 nm were prepared by radio frequency co-sputtering technique with glancing angle. The photoluminescence (PL) of the Au-SiO₂ crystal column film exhibited polarization characteristic. With an increase of the laser power, the slope ∂ log(PL intensity)/∂ log(laser power) changed from 2 to 3, which indicated that the PL of Au-SiO₂ crystal columns were induced by two- and three-photon absorption, respectively.     

A combined approach to fabricating Si nanocrystals with high photoluminescence intensity

This work demonstrates that by combining three methods with different mechanisms to enhance the photoluminescence (PL) intensity of Si nanocrystals embedded in SiO₂ (or Si-nc:SiO₂), a promising material for developing Si light sources, a very high PL intensity can be achieved. A 30-layered sample of Si-nc:SiO₂/SiO₂ was prepared by alternatively evaporating SiO and SiO₂ onto a Si(1 0 0) substrate followed by thermal annealing at 1100 °C. This multilayered sample possessed a fairly high PL efficiency of 14% as measured by Greenham's method, which was 44 times that of a single-layered one for the same amount of excess Si content. Based on this multilayered sample, treatments of CeF₃ doping and hydrogen passivation were subsequently applied, and a high PL intensity which was 167 times that of a single-layered one for the same amount of excess Si content was achieved.     

Photoluminescence characteristics of energy transfer between Er and Bi in Gd2O3: Er, Bi

The phosphors, Bi³⁺- activated Gd₂O₃:Er³⁺, were prepared by sol-gel combustion method, and their photoluminescent properties were investigated under ultraviolet light excitation. The emission spectrum exhibited sharp peaks at about 520, 535, 545, 550 and 559 nm due to (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions. The luminescent intensity was remarkably improved by the incorporation of Bi³⁺ ions under 340 nm light excitation, which suggested very efficient energy transfer from Bi³⁺ ions to Er³⁺ions. The introducing of Bi³⁺ ions broadened the excitation band of the phosphor, of which a new strong peak occurred ranging from 320 to 360 nm due to the 6s²→6s6p transition of Bi³⁺ ions. There is significant energy overlap between the emission band of Bi³⁺ ions and the excitation band of Er³⁺ ions. Under 340 nm light excitation, Bi³⁺ absorbed most of the energy and transferred it to Er³⁺. The energy transfer probability from Bi³⁺ to Er³⁺ is strongly dependent on the Bi³⁺ ion concentration. Also, the sensitization effectiveness was studied and discussed in this paper.     

GaAs nanocrystals: Structure and vibrational properties

GaAs nanocrystals were grown on indium tin oxide substrate by an electrodeposition technique. Atomic force microscopic measurement indicates an increase in the size of the nanocrystal with decrease in the electrolysis current density accompanied by the change in the shape of the crystallite. Transmission electron microscopic measurements identify the crystallite sizes to be in the range of 10-15 nm and the crystal structure to be orthorhombic. On account of the quantum size effect, the first optical transition was blue shifted with respect to the band gap of the bulk GaAs and the excitonic peak appeared prominent. A localized phonon mode ascribed to certain point defect occurred in the room temperature micro-Raman spectrum.     

Arresting photodegradation of porous silicon by a polymer coating

Light soaking in air rapidly decreases photoluminescence (PL) of porous silicon (PS) and increases electron spin resonance (ESR) signal. In vacuum, a short light exposure (<2700 s) increases PL and decreases ESR, but longer exposures again degrade the PL. We could arrest the light-induced degradation over long periods by applying a thin polymer coating, which resulted in constant PL and ESR intensities. The PL intensity of coated PS is comparable to the PL intensity of a fresh PS sample in air. FTIR spectrum suggests new bond formations at the PS/polymer interface that may be responsible for PL stability.     

Fabrication and optical properties of SnS thin films by SILAR method

Although the fabrication of tin disulfide thin films by SILAR method is quiet common, there is, however, no report is available on the growth of SnS thin film using above technique. In the present work, SnS films of 0.20 μm thickness were grown on glass and ITO substrates by SILAR method using SnSO₄ and Na₂S solution. The as-grown films were smooth and strongly adherent to the substrate. XRD confirmed the deposition of SnS thin films. Scanning electron micrograph revealed almost equal distribution of the particle size well covered on the surface of the substrate. EDAX showed that as-grown SnS films were slightly rich in tin component while UV-vis transmission spectra exhibited high absorption in the visible region. The intense and sharp emission peaks at 680 and 825 nm (near band edge emission) dominated the photoluminescence spectra.     

Photoluminescence of hexagonal boron nitride: Effect of surface oxidation under UV-laser irradiation

We report on the UV laser-induced fluorescence of hexagonal boron nitride (h-BN) following nanosecond laser irradiation under vacuum and in different environments of nitrogen gas and ambient air. The observed fluorescence bands are tentatively ascribed to impurity and mono (V_N) or multiple (m-V_N with m=2 or 3) nitrogen vacancies. A structured fluorescence band between 300 and 350 nm is assigned to impurity-band transition and its complex lineshape is attributed to phonon replicas. An additional band at 340 nm, assigned to V_N vacancies on surface, is observed under vacuum and quenched by adsorbed molecular oxygen. UV-irradiation of h-BN under vacuum results in a broad asymmetric fluorescence at ∼400 nm assigned to m-V_N vacancies; further irradiation breaks more B-N bonds enriching the surface with elemental boron. However, no boron deposit appears under irradiation of samples in ambient atmosphere. This effect is explained by oxygen healing of radiation-induced surface defects. Formation of the oxide layer prevents B-N dissociation and preserves the bulk sample stoichiometry.     

Synthesis and characterization of ZnS:Cu,Al phosphor prepared by a chemical solution method

A novel and simple synthesis route for the production of ZnS:Cu,Al sub-micron phosphor powder is reported. Both the host and activator cations were co-precipitated from an ethanol medium by mixing with a diluted ammonium sulfide solution. The co-precipitated ZnS:Cu,Al was in cubic zinc blende structure after an intermediate-temperature furnace annealing. Strong photoluminescent and cathodoluminescent (CL) emission were observed, which was attributed to the 3d¹⁰-3d⁹4s¹ radiative transition at those copper sites. At an accelerating voltage of 1 kV, the CL intensity of the co-precipitated ZnS:Cu,Al sample was recorded 94% of the commercial reference phosphor with the same composition made by high temperature solid-state-reaction method. The particle size of the co-precipitated phosphor powders was found to be controllable simply through adjusting the reactant concentrations. The particle size of the annealed samples was measured by dynamic light scattering, which showed a mean particle diameter between 200 and 700 nm depending on the co-precipitation conditions.     

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.