ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.     

Synthesis,characterization and photoluminescence of ZnO spindles by polyvinylpyrrolidone-assisted low-temperature wet-chemistry process

ZnO spindles were prepared by wet-chemistry process with surfactant polyvinylpyrrolidone at a low temperature of 35 °C. The morphologies and structures of the products were characterized by X-ray powder diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy. The addition of polyvinylpyrrolidone promoted the formation of ZnO crystal nuclei, and accelerated the growth rate of (0001) plane rich in Zn²⁺ ions. The as-obtained ZnO spindles were twin crystal wurtzite structures, with the size of 30 nm at the tips, 350–450 nm at the center, and 1–1.5 μm in length. The room-temperature photoluminescence results showed that surface effects played a major role in the luminescence of the ZnO spindles, which exhibited a broad violet–blue–green emission band related to deep level defects. We proposed a new growth mechanism, which might be useful for applications in synthesis of size- and shape-controlled ZnO crystals.     

Adjusting the porous and structural properties of mesoporous silica by the addition of organic modifiers

The effects of the organic modifiers 2-cyanoethyltriethoxysilane and 3-aminopropyltriethoxysilane on the porous properties of silicates synthesised by co-condensation with tetraethyl orthosilicate were investigated. Materials were synthesised in aqueous solutions of cetyltrimethylammonium bromide or n-dodecylamine surfactants. Preparations using cetyltrimethylammonium bromide and sodium hydroxide gave MCM-48, with an average pore diameter of 25 Å, while addition of 10 mol% (of total silica) 2-cyanoethyltriethoxysilane improved the mesoporosity characteristics; the modified preparation gave a more intense X-ray diffraction pattern confirming a more ordered structure with a greater volume of regular mesopores. Disordered materials with pores 145 Å in diameter were formed using 2-cyanoethyltriethoxysilane modifier and ammonia as base. All preparations incorporating 3-aminopropyltriethoxysilane modifier were disordered and microporous. For silicates synthesised using n-dodecylamine surfactant, mesopores with diameter 118 Å were formed using 2-cyanoethyltriethoxysilane while preparations with 3-aminopropyltriethoxysilane and in the absence of a modifier were microporous. The particle sizes of the silicates displayed a clear correlation with the pore diameters: microporous silicates were 0.5–1 μm in particle diameter, MCM-48 phase (25/27 Å) were 1–2 μm, while relatively large mesoporous materials (>100 Å) had particle dimensions 10–100 μm.     

Hydrothermal synthesis and characterization of VO2 (B) nanorods array

Highly ordered nanorods array of B phase vanadium dioxide was firstly synthesized with n-butanol as the reducing agent via a simple hydrothermal method without using template. The samples have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). The size of VO₂ (B) nanorods has the dimension of 50–100 nm in diameter and about 1–5 μm in length. The samples were measured as electrode materials by charge–discharge technique and the VO₂ (B) nanorods array demonstrated a high specific capacity of 520 mAh/g at 0.2 C. The influence of reaction temperature on fabricating nanorods array has been studied. The possible growth mechanisms of formation of nanorods and assembly of array were discussed.     

Growth and conductivity enhancement of N-doped ZnO nanorod arrays

A simple two-step process was developed for growing the nitrogen-doped ZnO (NZO) nanorod arrays on glass substrates. ZnO particles serve as a seed layer deposited by the electrostatic spray deposition method for the growth of NZO nanorods in aqueous solution. FE-SEM images revealed that nanorods have approximately uniform length distribution with hexagon end planes and grow vertically along the c-axis, which was also confirmed by X-rays diffraction. In addition, NZO nanorods had an average diameter of 140±20 nm and an average length of 1.2 to 2.7 μm with a wurtzite-type structure of ZnO. N doping had no prominent effect on the structure and crystal orientation, but it helps to increase the length and reduction in the diameter of nanorods. Moreover, electrical resistivity was found to decrease first and then increase with further nitrogen doping due to the decrease of mobility and increase of carrier concentration. Also the transmittance increased initially, but at higher nitrogen contents it decreased. Annealing the nanorods imparts no effect on the morphology, but there was a significant decrease in electrical resistivity due to the formation of oxygen vacancies. The realization of p-type ZnO nanorod arrays with durable and controlled transport properties is important for the fabrication of nanoscale electronic and optoelectronic devices.     

2 μm spectroscopic investigation of Tm3+-doped tellurite glass fiber

TmF₃ doped TeO₂–ZnO–La₂O₃ (TZL) glasses and fibers have been prepared by the conventional melt-quenching and suction casting methods, respectively. 2 μm emission properties and energy transfer mechanisms of the TZL glasses and fibers have been analyzed and discussed. The oscillator strength, Judd–Ofelt parameters, radiative transition probability and radiative lifetime of Tm³⁺ have been calculated based on the absorption spectra and Judd–Ofelt theory. The maximum emission cross-section of Tm³⁺ is 6.9 × 10^?21 cm² near 2 μm. Emission spectra have been obtained from both TZL fibers and bulk glass when excited with a 794 nm pump. The results of 2 μm emission spectra indicate that the line width of Tm³⁺ measured in fibers is narrower than that in the bulk glass sample. The peak position of the emission spectra shifts to longer wavelength with increment of the fiber length.     

Chalcogenide step index and microstructured single mode fibers

Chalcogenide glasses are known for their large transparency in the mid infrared, which includes the two atmospheric windows lying from 3–5 μm and 8–12 μm. Chalcogenide single mode fibers present numerous potential applications in the IR field, such as military countermeasures, LIDAR spectroscopy and spatial interferometry. Two routes can be considered for the elaboration of a single mode fiber. The first method consists in preparing a classical step index fiber (SIF) with a core-clad configuration. This procedure is based on two glass compositions (core and clad) with compatible thermal and optical properties and having a refractive index difference allowing the single mode propagation. The second route is based on the design of a microstructured optical fiber (MOF) in which the guiding function is ensured by the refractive index contrast between the core glass and the air contained in the capillaries surrounding the core. Two kinds of fibers exhibiting single mode propagation were fabricated; the first one is a SIF with a 22 μm core diameter and the second one is a three rings of holes MOF. The geometry of the MOF shows a d/Λ around 0.35 and a 40 μm core diameter. In both cases the optical losses in the 2 to 12 μm region were measured and compared.     

Growth and characterization of the chalcopyrite LiGaTe2: A highly non-linear birefringent optical crystal for the mid-infrared

LiGaTe₂ crystals have been grown by the Bridgman–Stockbarger technique. The clear transparency range of LiGaTe₂ extends from 2.5 to 12 μm and its band-gap at room temperature is at 2.41 eV (515 nm). LiGaTe₂ is a positive uniaxial crystal which possesses sufficient birefringence for phase-matching. Its non-linear coefficient d₃₆ estimated by phase-matched second harmonic generation is 43 pm/V ± 10% at 4.5 μm. The properties of LiGaTe₂ are compared to those of other mid-IR chalcopyrite non-linear optical crystals with special emphasis on the frequency doubling potential for CO₂ lasers operating at 10.6 μm.     

A large core microstructured fluoride glass optical fibre for mid-infrared single-mode transmission

A microstructured optical fibre based on an alumino-zirco-chloro-fluoride glass has been fabricated in which the light-guiding structure comprises a single ring of air-holes, machined directly into the preform rod using an ultrasonic drill around a large effective solid core. The objective was single-moded transmission of longer mid-infrared wavelengths at high laser power without causing radiation damage to the fibre material. It has been demonstrated that this fibre preserves high laser beam quality and can transmit wavelengths between 2.1 and 4.7 μm, single-moded in an effective core of diameter 79 μm. Optical fibre transmission losses from 1.4 to 10.3 dB m^?1 have been measured over this wavelength range. No damage was observed in the fibre at peak pulse power, setting a lower limit of >1 GW cm^?2 for the laser damage threshold. Brightness was preserved at wavelengths longer than 4 μm.     

Optical properties of novel PbS and PbSe quantum-dot-doped alumino-alkali-silicate glasses

Lead sulfide PbS and lead selenide PbSe quantum dots (QDs) were synthesized in novel alumino-alkali-silicate glass. The synthesis of the nanocrystals was stabilized by introduction of two alkaline components. The presence of crystalline phase was confirmed by X-ray diffraction analysis, transmission electron microscopy and optical spectroscopy. For PbS (PbSe) QD-doped glass, the position of the 1S–1S excitonic absorption peak can be managed in the spectral range of 1.5–2.1 μm (for PbS) or 1.8–2.2 μm (for PbSe) by appropriate heat‐treatment mode. The corresponding QD average diameter was found to be 5.8–9.7 nm (for PbS) and 7.5–9.5 nm (for PbSe). The influence of the secondary heat-treatment at the temperatures of 490–525 °C on the PbS QD growth in the glass matrix initially treated at 480 °C was studied in details. The photoluminescence of the PbS-QD-doped glass was observed, it was referred to the radiative recombination of the excitons from the 1S–1S state. The possibility to obtaining narrow 1S–1S absorption lines at the wavelengths longer than 2 μm is discussed.     

Characterization of pure ZnO thin films prepared by a direct photochemical method

In this paper, amorphous ZnO thin films were obtained by direct UV irradiation of β-diketonate Zn(II) precursor complexes spin-coated on Si(1 0 0) and fused silica substrates. ZnO films were characterized by means of XPS, X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). These analyses revealed that as-deposited films are amorphous and have a rougher surface than thermally treated films. Optical characterization of the films showed that these are highly transparent in the visible spectrum with an average transmittance of up to 95% over 400 nm, and an optical band-gap energy of 3.21 eV for an as-deposited film, and 3.27 eV for a film annealed at 800 °C. Low resistivity values were obtained for the ZnO films (1.0 × 10⁻² Ω cm) as determined by Van der Pauw four-point probe method.     

Phase separation in Ag–Ge–Se glasses

Field emission-scanning electron microscopy (FE-SEM) and electric force microscopy (EFM) measurements were carried out on bulk Ag_x(Ge_0.25Se_0.75)_100−x glasses with x = 5 and 15 at.%. The presence of chemical contrasts and electrical inhomogeneity throughout the samples indicated that the glasses were phase separated. Moreover it appears that while silver-rich nodules of ∼1 μm were embedded in a silver-poor connecting phase in the glass containing 5 at.% Ag, it was the opposite that occurred in the glass containing 15 at.% Ag. Such an inversion explains the large difference of seven orders of magnitude in the conductivity of the two glasses.     

The effect of copper ions addition on structural and optical properties of zinc borate glasses

Glasses in the ternary system xCuO?(100 ? x)[55B₂O₃·45ZnO] (0 ≤ x ≤ 20 mol%) have been prepared by melting at 1200 °C and rapidly cooling at room temperature. The effect of copper ions addition in 55B₂O₃·45ZnO glass matrix together with the matrix effect on paramagentic behavior has been investigated using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, differential thermal analysis (DTA), electron paramagnetic resonance (EPR), ultraviolet–visible (UV–VIS) spectroscopy and density measurements. The increase of the number of non-bridging oxygen (NBO) atoms as a function of CuO content in these glasses leads to the decrease of glass polymerization which reduces the stability of the glasses and favors the association of copper ions in clusters. This leads to the major changes of structural and optical properties of the studied glasses as can be seen from the data obtained by FTIR and EPR spectroscopies.     

High refractive index contrast in fused silica waveguides by tightly focused,high-repetition rate femtosecond laser

A new domain of optical waveguide writing with record high refractive index contrast (0.022) is reported in fused silica by strong focusing of a 522 nm wavelength, 500 kHz repetition rate femtosecond laser with oil-immersion optics. The strongly confining waveguide supports a mode of only 7 μm mode field diameter at 1550 nm wavelength, opening the door for higher density integration in photonic circuits formed by femtosecond lasers. It is found that green and fundamental wavelengths have similar absorption in femtosecond laser waveguide writing in fused silica and that the advantage of the second harmonic is simply from an increased fluence through a smaller focal volume.     

Growth of pure ZnO thin films prepared by chemical spray pyrolysis on silicon

Structural, morphological, optical and electrical properties of ZnO thin films prepared by chemical spray pyrolysis from zinc acetate (Zn(CH₃COO)₂ 2H₂O) aqueous solutions, on polished Si(1 0 0), and fused silica substrates for optical characterization, have been studied in terms of deposition time and substrate temperature. The growth of the films present three regimes depending on the substrate temperature, with increasing, constant and decreasing growth rates at lower, middle, and higher-temperature ranges, respectively. Growth rate higher than 15 nm min⁻¹ can be achieved at T_s=543 K. ZnO film morphological and electrical properties have been related to these growth regimes. The films have been characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy.     

Preparation of transparent cobalt doped glass ceramic and application as saturable absorber Q switch for 1.54 μm Er-glass laser

Glass with composition of 51SiO₂–24.5Al₂O₃–23MgO–1.5K₂O doped with Co²⁺ ions was prepared by conventional melting method. The glass sample was heated at 900 °C for 360 min under atmosphere, and the powder XRD measurement showed that crystalline phase successfully precipitated in the sample. As is compared with standard JCPDS card, the crystalline phase identified as a mixture of zirconium titanate (ZrTiO₄) and one of the compounds of magnesium aluminum oxide. The crystallite size was confirmed by transmission electron microscope (TEM) observation; it could be estimated as 30 nm in diameter from the TEM image. Based on the area ratio of crystalline phase and residual glass phase, the precipitated crystallite phase volume ratio can be estimated to be not higher than 30% in the Co²⁺ doped glass ceramic sample. The absorption coefficient at 1.54 μm for transparent glass ceramic sample is clearly higher than that in base glass, which can be explained by the fact that Co²⁺ ions entered into the precipitated nano-sized crystal phase and led to higher absorption coefficient at 1.54 μm for tetrahedral coordinated Co²⁺ ion. Consequently, the Co²⁺ doped transparent glass ceramic sample with thickness of 0.35 mm was used as a saturable absorber for 1.54 μm Er-glass laser oscillation, and Q switched pulses with pulse energy of 40 mJ, pulse width of 42 ns, and peak power of 0.95 mW were shown in the experiments.     

Investigation of directional solidified Al–Ti alloy

Al–1 wt% Ti alloy was directionally solidified upwards under argon atmosphere under the two conditions; with different temperature gradients (G = 2.20–5.82 K/mm) at a constant growth rate (V = 8.30 μm/s) and with different growth rates (V = 8.30–498.60 μm/s) at a constant temperature gradient (G = 5.82 K/mm) in a Bridgman furnace. The dependence of characteristic microstructure parameters such as primary dendrite arm spacing (λ₁), secondary dendrite arm spacing (λ₂), dendrite tip radius (R) and mushy zone depth (d) on the velocity of crystal growth and the temperature gradient were determined by using a linear regression analysis. A detailed analysis of microstructure development with models of dendritic solidification and with previous similar experimental works on dendritic growth for binary alloys were also made.     

Directional role of weak magnetic field on the self-fabrication of ordered nickel chains

Novel ordered nickel chains with diameter 250–500 nm and length more than 5 μm were synthesized under weak magnetic field by hydrazine reducing in ethylene glycol. The phase, morphology and magnetic properties were characterized by X-ray diffraction (XRD), scanning electron microanalyzer (SEM) and vibrating sample magnetometer (VSM), respectively. The results reveal that weak magnetic field leads to the fabrication of nickel chains paralleling each other with hierarchical structures. The growth mechanism and fabrication process of nickel magnetic nanocrystallites were discussed.     

Self-catalyzed vapor–liquid–solid growth of InP/InAsP core–shell nanopillars

Indium phosphide/indium arsenide phosphide core–shell nanopillars have been prepared by the vapor–liquid–solid method using liquid indium droplets as the catalyst. The indium droplets were generated in situ in the deposition reactor. The hexagonal nanopillars exhibited hexagonal shaped sidewalls with average width and height of 150 and 250 nm, respectively. Cross-section transmission electron microscopy with selected area electron diffraction and X-ray dispersion energy analysis verified that an InAsP layer, approximately 10 nm thick, coated the pillars. Photoluminescence spectra at 77 K yielded an extremely intense band at 0.76 eV (1.63 μm), which was due to the InAsP shell on the pillars.     

Use of sandwich structures with ZnO:Al transparent electrodes for the measurement of the electro-optic properties of standard and fluorinated poled copolymers at λ = 1.55 μm

We report on the measurement of the electro-optic coefficient r₃₃ of poled polymers at λ = 1.55 μm via the non-linear ellipsometry technique (or Teng and Man technique). Since the measurements rely on the use of sandwich structures with transparent electrodes, different types of aluminium doped zinc oxide (ZnO:Al) are taken into account in order to ensure transparency at the infrared range wavelength. Results on the disperse red 1/poly-methyl-metacrylate (DR1–PMMA) based side-chain benchmark system, with several different concentrations of active groups from 0.05 to 0.58 molar, are reported and demonstrate the reliability of the technique. The measurement technique was then used to evaluate the r₃₃ coefficient of copolymers derived from DR1–PMMA by partial fluorination (FATRIFE). In this case, we measured copolymers with three concentrations of active groups, 0.30, 0.37 and 0.56 molar.