Catalyst-free synthesis and luminescence of aligned ZnO nanorods

Quasi-aligned undoped ZnO nanorods with diameter in the range 100–300 nm and length of several micrometers have been grown catalyst-free on Si(1 0 0) wafer in a one-step process by direct heating of Zn powders. All nanowires are single crystals and are aligned vertically to the substrate surface with c-axis preferred orientation. XRD, HRTEM and Raman studies revealed that the ZnO nanorods have wurtzite phase, are highly crystalline and well aligned with the lattice parameters a=0.32 nm and c=0.52 nm. The PL spectra measured at different temperatures are dominated by excitonic emission at 380 nm and less intense below band gap emission band centered at 520 nm.     

Effect of ratios of Cd:Se in CdSe nanoparticles on optical edge shifts and photoluminescence properties

This paper addresses the issue related to morphology of CdSe nanoparticles capped with organic molecules. Semiconducting CdSe nanoparticles of 5–16 nm are synthesized using CdO precursor, capped with trioctyl phosphine (TOP)/trioctyl phosphine oxide (TOPO) using different starting precursor ratios of Cd:Se. At an optimum ratio of Cd/Se-2:1, highly luminescent and small sized (5 nm) nanoparticles are obtained. At other Cd/Se precursor ratios (0.5:1, 1:1, 3:1) larger particles are formed with varying photoluminescence (PL) intensity and optical absorption (UV–VIS). X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) are used to determine the crystallinity and stoichiometry of the system, respectively. It is shown that the blue shifts of the optical absorption edge concurrent with the CdSe nanocrystal size reduction, for sizes measured by XRD with respect to the bulk semiconductor, agree perfectly with the strong quantum confinement model. The optical edge shifts are significantly higher for CdSe nanocrystallite as measured by transmission electron microscopy (TEM) than the theoretical prediction based on the strong quantum confinement model. This is understood on the basis of agglomeration effects as observed by TEM for CdSe nanocrystallites. The nano-sized CdSe growth island thus formed comprises of several TOP/TOPO passivated nanocrystals.     

Nucleation, growth and morphology of Co thin films on Ag(1 1 0)

Scanning tunneling microscopy (STM) experiments reveal that Co growth on Ag(1 1 0), at coverages of Co < 1 ML and low substrate temperatures (150 K), involves a concomitant insertion of Co into the top Ag layer and exchange of Ag out onto the surface. At 300 K, coverages of Co > 1 ML gives rise to a 3D nanocluster growth on the surface, with the clusters covered by Ag. Depending slightly on coverage, the clusters have a typical diameter of 3 nm and a height of 0.4 nm. Upon annealing to 500 K, major changes are observed in the morphology of the surface. STM and AES show that there is a reduction of the number of Co islands on the surface, partly due to subsurface Co cluster migration and partly due to sintering into larger clusters.     

Temperature dependent photoluminescence from ZnO/MgZnO multiple quantum wells grown by pulsed laser deposition

We have studied temperature dependent photoluminescence (PL) from ZnO Multiple Quantum Wells (MQWs) of different well layer thicknesses in the range 1–4 nm grown on (0001) sapphire by a novel in-house developed buffer assisted pulsed laser deposition. At 10 K the PL peak shifted toward blue with decreasing well layer thickness and at constant well layer thickness the PL peak shifted towards red with increasing temperature. To the best of our knowledge we have observed for the first time an efficient room temperature (RT) PL emanating from such MQWs. The red shift of the PL peak with increasing temperature has been found to be due to the band gap shrinkage in accordance with the Varshni’s empirical relation. The spectral linewidth was found to increase with increasing temperature due to the scattering of excitons with acoustic and optical phonons in different temperature regimes. Both at RT and at 10 K the PL peak shifted with respect to the well layer thickness in the range of 3.35–3.68 eV with decreasing thickness in agreement with the calculated values.     

The size distributions of nanoparticles of the oxides of Mg, Ba and Al in flames: Their measurement and dependence on the concentrations of free radicals in the flame

Flat, pre mixed, laminar, and very O₂-rich flames of C₂H₂ + O₂ + N₂ with [O₂]/[O₂]_stoich  2.8 and a temperature 2000 K have been burned at atmospheric pressure. Trace amounts (13 ppm) of the metals Mg, Ba or A1 were added to the unburnt gases by nebulising an aqueous solution of a halide of the metal, so that e.g., Mg formed molecules of Mg(OH)₂, MgOH and MgO, as well as free atoms of Mg. The relative abundances of these species were governed by well-characterised equilibria and consequently depended on the temperature and also the concentrations of the flame’s free radicals H, OH and O. Transmission electron microscopy showed that nanoparticles of the oxides of these metals formed from their pool of molecular species in these flames. Particle size distributions were also measured (much less tediously) with a mobility analyser (DMS 500, Cambustion) operating at 0.25 bara. The optimal way of continuously sampling the gases at a point along the flame’s axis was investigated and shown to require expanding the sample (to a pressure of 1/3 bara) supersonically through an orifice with a diameter greater than 0.4 mm. In addition, the sample had to be diluted with N₂, with a volumetric flow rate of 10–20 times that of the sample, all at 1/3 bara. The sizes of oxide nanoparticles, as measured by transmission electron microscopy, agreed with the values of 6–10 nm from the mobility analyser. With Mg all the metal appeared very rapidly as nearly spherical nanoparticles of MgO early in a flame’s reaction zone. This was also true for Ba, which, according to thermodynamic considerations at the final temperature of the flame, should not form any particles of BaO. That particles do actually form is due to the reaction zone having a relatively low temperature and super-equilibrium concentrations of the free radicals H, OH and O. Aluminium was expected to form particles of A1₂O₃. However, only a small fraction of the Al formed particles; this is attributed to the production of gas-phase molecules of Al₂O₃ (i.e., the nuclei) from AlO and AlO₂ being by a relatively slow three-body reaction, as well as Al₂O₃ being a very minor member of the gas-phase pool of molecular species containing Al.     

Carbon nanotube–polymer composites for photonic devices

We report the fabrication of high optical quality single wall carbon nanotube polyvinyl alcohol composites and their application in nanotube based photonic devices. These show a broad absorption of semiconductor tubes centred at 1.55 μm, the spectral range of interest for optical communications. The films are used as mode-lockers in an erbium doped fibre laser, achieving 700 fs mode-locked pulses. Raman spectroscopy shows no damage after a long time continuous laser operation.     

Picosecond optical parametric amplification of stimulated Raman as high peak-power source and ultra-sensitive preamplifier

We report the characteristics of the amplified stimulated Raman scattering (SRS) pulses generated in liquid benzene by a picosecond (ps) β-barium borate (BBO) optical parametric amplifier (OPA). When the OPA system was used as an energy amplifier for SRS pulses, with a pump energy of 2.4 mJ at 355 nm for the OPA, the maximum output energy of the amplified SRS was about 0.73 mJ for the signal and 0.18 mJ for the idler, the energy conversion efficiency was 30.4% from the pump beam to the amplified third order Stokes component at 635.1 nm. The total efficiency would be as high as 37.9% if the output of the idler is also included. The corresponding spectral line width of the amplified Raman pulse was 11.8 cm⁻¹ with a pulse width of 10.9 ps and a peak power of 67 MW. The OPA system was also used as an amplifier for very weak Raman signal, the slope gain factor of this amplifier was found to be as high as 4.1 × 10⁷ and the energy detection limit was as low as 14.8 aJ per pulse, or 48 photons at 635.1 nm, in particular. Such a detection limit corresponds to approximately 0.5 photons per pulse if the time-gate of the OPA is reduced to 150 fs and it is about the same as or even better than a recently report on the 0.75 photons detection limit for a 150-fs OPA of coherent signal at 800 nm.     

The electrodeposition of copper onto UHV-prepared GaAs(0 0 1) surfaces

Synchrotron surface X-ray diffraction has been used to investigate in situ the morphology and epitaxy of monolayer amounts of copper electrodeposited from aqueous electrolyte onto ultra-high vacuum prepared, smooth, Ga- or As-terminated GaAs(0 0 1) surfaces. The fcc lattice of the epitaxial Cu islands is rotated by 5° and tilted by about 9° with respect to the GaAs substrate lattice, leading to eight symmetry equivalent domains of Cu islands terminated by {1 1 1} facets.     

Structure and reaction pathways of methyl lactate on Pd(1 1 1)

The adsorption and reaction of methyl lactate (CH₃CH(OH)COOCH₃) is studied in ultrahigh vacuum on a Pd(1 1 1) surface using temperature-programmed desorption (TPD) and reflection–absorption infrared spectroscopy (RAIRS). Methyl lactate reacts at relatively low temperatures (220 K) by O–H bond scission. This intermediate can either react with hydrogen to reform methyl lactate at 280–300 K or undergo β-hydride elimination to form flat-lying methyl pyruvate. This decomposes to form acetyl and methoxy carbonyl species as found previously following methyl pyruvate adsorption on Pd(1 1 1). These species predominantly react to form carbon monoxide, methane and hydrogen.     

Growth mechanism and optical property of CdS nanoparticles synthesized using amino-acid histidine as chelating agent under sonochemical process

Using amino-acid histidine as chelating agent, CdS nanoparticles have been synthesized by sonochemical method. It is found that by varying the ultrasonic irradiation time, we can tune the band gap and particle size of CdS nanoparticles. The imidazole ring of histidine captures the Cd ions from the solution, and prevents the growth of the CdS nanoparticles. The deviation in the linear relation in between cube of radius of nanoparticles and ultrasonic irradiation time confirms the growth of CdS nanoparticles occur via two process; one is the diffusion process of the reactants as well as reaction at the surface of the crystallite. CdS nanoparticles synthesized using histidine as organic chelating agent have band edge emission at 481 nm and have greater photoluminescence intensity with blue-shift to higher energy due to typical quantum confinement effect.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

Quantum confinement and interface structure of Si nanocrystals of sizes 3–5 nm embedded in a-SiO2

Spectroscopic ellipsometry and Monte Carlo simulations are employed to answer the fundamental question whether the energy gaps of Si nanocrystals with sizes in the range of 3–5 nm, which are embedded in amorphous silica, follow or deviate from the quantum confinement model, and to examine their interfacial structure. It is shown that the optical properties of these nanocrystals are well described by the Forouhi–Bloomer interband model. Analysis of the optical measurements over a photon-energy range of 1.5–5 eV shows that the gap of embedded nanocrystals with a mean size of 3.9 nm follows closely quantum confinement theory. A large band gap expansion (0.65 eV) compared to bulk Si is observed. The Monte Carlo simulations reveal a non-abrupt interface and a large fraction of interface oxygen bonds. This, in conjunction with the experimental observations, indicates that oxygen states and the chemical disorder at the interface have a negligible influence on the optical properties of the material in this size regime.     

Arsenic-related recombination in MOVPE-grown ZnO/GaAs films

In this paper, ZnO films grown by metalorganic vapour phase epitaxy on various substrates (GaAs, silicon, sapphire) and using different VI /II ratios, are investigated by photoluminescence (PL) spectroscopy. The PL spectra of layers grown on GaAs show significant recombination at 3.320 eV, 3.305 eV and 3.270 eV. These energies are remarkably similar to what have been reported for hybrid beam deposited ZnO:As [Y.R. Ryu, T.S. Lee, H.W. White, Appl. Phys. Lett. 83 (2003) 87] and arsenic-implanted ZnO crystals [T.S. Jeong, M.S. Han, C.J. Youn, Y.S. Park, J. Appl. Phys. 96 (2004) 175], and the lines are ascribed to the incorporation of arsenic, which diffuses from the substrate into the films. Two acceptor levels are deduced at 120 meV and at 140–150 meV.     

Optical properties of citrate-stabilized CdS nanoparticles

Citrate-stabilized CdS nanoparticles of size 4 nm are obtained by varying the sulfide:citrate ion concentration in a simple aqueous synthesis method. The optical absorption and photoluminescence properties of the nanoparticles are studied. The size of the crystallites is found to be less affected by sulfide:citrate ratio. At lower concentrations of S²⁻, trap state emission is favoured and at higher concentrations excitonic transition is predominant as shown by optical absorption and photoluminescence spectra. Effective surface capping and optimum concentration of S²⁻ leads to the quenching of surface-defect-related emission. Increase in citrate ion concentration is found to increase the intensity of photoluminescence band arising from trap state emission revealing the role of sulfide:citrate ratio on surface modification of CdS nanocrystals. The nanoparticles are hexagonal as shown by the X-ray diffraction and selected area electron diffraction pattern.     

Spectroscopic investigation of arsenate and selenate incorporation into hydroxylapatite

The mechanism(s) of arsenate and selenate incorporation into hydroxylapatite (HAP) using extended X-ray absorption fine structure (EXAFS) spectroscopy was investigated for As- and Se-doped HAP samples with concentrations between 200 and 2500 ppm. EXAFS data on As and Se K-edges have shown similar local coordination environments and are similar to that of P in HAP, suggesting the substitution of arsenate or selenate tetrahedra on the phosphate sites. EXAFS best-fitting for As-doped samples shows that the first shell is fitted with approximately 4 O atoms at 1.68 Å, showing As(V) in tetrahedral coordination, and Se K-edge EXAFS data are characterized by the backscattering contributions an oxygen shell at 1.2 Å in the Fourier transform, which can be fit with 4 O atoms at 1.65 ± 0.01 Å. This is characteristic of Se–O distances in SeO₄ tetrahedron. These findings suggest that arsenate and selenate substitute for phosphate groups with local distortions during the incorporation of these metals into the structure of HAP.     

Photonic generation of microwave signal using a dual-wavelength single-longitudinal-mode distributed Bragg reflector fiber laser

In this paper, a novel all-optical microwave generation technique based on a dual-wavelength single-longitudinal-mode (SLM) distributed Bragg reflector (DBR) fiber laser is proposed and demonstrated. By exploiting spatial hole burning (SHB) effect, this laser could provide stable dual-wavelength SLM operation with a wavelength separation of 0.088 nm corresponding to the microwave signal at 10.484 GHz with a 3 dB bandwidth of 28 kHz. By appropriately adjusting the pump power, dual-wavelength oscillation could be maintained at different temperatures. We have theoretically analyzed the mechanism for microwave generation of the proposed DBR laser, and the calculated microwave frequency is in good agreement with our experimental results. Furthermore, experimental observation shows both of the laser wavelengths and generated microwave signals have good stability at room temperature.     

Structure and properties of the one-dimensional cobalt oxide CaCo2O4

We have studied crystal structure and transport properties of the quasi one-dimensional cobalt oxide CaCo₂O₄. The CaCo₂O₄ phase crystallizes in calcium-ferrite type structure, which consists of a corner- and edge-shared CoO₆ octahedron network including one-dimensional double chains. Large thermoelectric power (S  150 μV/K at 390 K) with metallic temperature dependence of S, moderate resistivity (ρ  2.9 × 10⁻¹ Ω cm at 390 K) with carrier localization at low temperature, and normal thermal conductivity (κ  6.3 W/Km at 390 K) were observed. The phonon mean-free path was calculated from the observed data, as a function of temperature. The long phonon mean-free path (l  24 Å at 300 K) implies that the thermal conductivity could be suppressed by impurity scattering of phonons with partial element substitution.     

Quantum confinement effect in ZnO nanoparticles synthesized by co-precipitate method

Quantum mechanical effects such as an increased bandgap of semiconductors with reduction of size are viewed as having strong potential for future applications. In the present work, zinc oxide (ZnO) nanoparticles (NPs) were synthesized via the co-precipitate method. Very narrow particle size distribution of the ZnO nanoparticles was achieved through careful control of the synthesis conditions. The structural, morphological, and optical characterization was carried out using X-ray diffraction, atomic force microscopy, and UV–vis reflectance techniques, respectively. The results indicated that increasing the temperature from 60 to 65 °C caused a subsequent increase in particle size from 4 to 12 nm. An associated increase in bandgap with decrease in particle size was also noticed which is a strong indication of the quantum confinement effect.     

Structural properties of Cu clusters on Si(1 1 1):Cu2Si magic family

Basing on the results of the scanning tunneling microscopy (STM) observations and density functional theory (DFT) calculations, the structural model for the Cu magic clusters formed on Si(1 1 1)7 × 7 surface has been proposed. Using STM, composition of the Cu magic clusters has been evaluated from the quantitative analysis of the Cu and Si mass transport occurring during magic cluster converting into the Si(1 1 1)‘5.5 × 5.5’-Cu reconstruction upon annealing. Evaluation yields that Cu magic cluster accommodates 20 Cu atoms with 20 Si atoms being expelled from the corresponding 7 × 7 half unit cell (HUC). In order to fit these values, it has been suggested that the Cu magic clusters resemble fragments of the Cu₂Si-silicide monolayer incorporated into the rest-atom layer of the Si(1 1 1)7 × 7 HUCs. Using DFT calculations, stability of the nineteen models has been tested of which five models appeared to have formation energies lower than that of the original Si(1 1 1)7 × 7 surface. The three of five models having the lowest formation energies have been concluded to be the most plausible ones. They resemble well the evaluated composition and their counterparts are found in the experimental STM images.     

Fabrication of well-defined individual dislocations in SiGe as a novel one-dimensional system

We show a new way to fabricate well-defined individual dislocations in SiGe. We started with a fully pseudomorphic but metastable SiGe layer grown on Si(0 0 1) by molecular beam epitaxy. Next, elongated (1 mm) mesa stripes with various widths (0.5–3 μm) were fabricated by a combination of isotropic and anisotropic etching. For smaller stripes, elastic relaxation of the strained SiGe layer can occur, transforming the originally biaxial strained layer into uniaxial strained subsystems. Subsequent strain relaxation caused by high temperature treatments leads to the formation of individual dislocation along the mesa stripes. The number of parallel dislocation can be adjusted by the original strain (Si:Ge ratio and layer thickness) and the mesa widths. We were able to fabricate structures with exactly one dislocation. Finally, contact pads were added to the stripes enabling the electrical characterization of individual dislocation.