Characterization of nanocluster formation in Cu-implanted silica: Influence of the annealing atmosphere and the ion fluence

High-purity silica plates were implanted with 2 MeV Cu⁺ ions at various ion fluences: 0.7 × 10¹⁶, 3 × 10¹⁶ and 6 × 10¹⁶ ions/cm². After implantation, thermal treatments were performed at 400 °C and 900 °C in either an oxidizing (air) or a reducing (50% H₂ + 50% N₂) atmosphere for 1 h. All the samples were studied by electron paramagnetic resonance, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy (HRTEM), Rutherford backscattering spectrometry and optical absorption. The advantages of the reducing atmosphere (RA) over the oxidizing atmosphere (OA) are clearly observed. When annealed in a RA, the surface plasmon resonance is more intense and a narrower size distribution of the Cu nanoparticles is obtained. The existence of CuO nanoparticles was confirmed by HRTEM, and while both annealing atmospheres favor the formation of CuO nanoparticles, this process is strengthened when the sample is annealed in an OA.     

Diffusion of chromium in chrysoberyl

Cr³⁺ diffusion in chrysoberyl (BeAl₂O₄) irradiated by H⁺ ions and electrons has been studied and compared with diffusion in non-irradiated samples. Chrysoberyl crystals were irradiated with 6 MeV H⁺ ions to fluencies of 1×10¹⁶ cm^–2 for 25 min and with 10 MeV electrons to fluencies of 2×10¹⁷ cm^–2 for 1 h. Three different types of samples, which were doped with Cr³⁺, were annealed in horizontal alumina tube furnaces by 50 K intervals in the temperature range from 1773 to 1923 K for 200 h. Scanning electron microscope–energy dispersive X-ray spectrometer (SEM–EDX) was used to measure the diffusion. Arrhenius equations for the diffusion coefficient for Cr³⁺ in the temperature range 1773–1923 K were developed:     

Fluorinated nanoporous SiO2 films with ultra-low dielectric constant

Fluorinated nanoporous silica (denoted as SiO₂:F) thin films with low dielectric constant were prepared by a sol-gel method and spin coating technique. The leakage current densities of the SiO₂:F thin films were 10⁻⁸ and 3 × 10⁻⁶ A/cm² respectively for the as-deposited films and for those subjected to annealing at a temperature of 450 °C. These currents are more than one order of magnitude lower than those of the common SiO₂ films. Photoluminescent results showed strong blue-light emission and a small blue shift in the SiO₂:F films that were related to the increment of the porosity. The dielectric properties were also characterized and the k value of the annealed SiO₂:F film was found to be about 1.67. The hole size in the films is small and the size distribution is uniform for the annealed SiO₂:F samples due to the effects of fluorination. The underlying mechanism for fluorination is discussed in this paper.     

Optical properties of Cr ion in lithium metasilicate Li2O · SiO2 transparent glass-ceramics

The optical properties of Cr³⁺ ions in lithium metasilicate (Li₂O · SiO₂) transparent glass-ceramics were investigated. The main crystalline phase precipitated was the lithium metasilicate (Li₂O · SiO₂) crystal. The percent crystallinity and crystalline size were ranging 65-75% and 20-35 nm, respectively. The color changes drastically to deep pink from emerald green upon crystallization. New and strong absorption bands appeared and the absorption intensity increases by about 10 times that in glass. These new absorption bands are found to be derived from Cr³⁺ ions in octahedral sites in the lithium metasilicate crystal lattice. Cr³⁺ ions substitute for three Li⁺ ions and occupy the distorted octahedral site between single [SiO₄]_n chains of lithium metasilicate crystal. The ligand field parameters can be estimated: 10Dq = 13 088 cm⁻¹, B = 453 cm⁻¹, Dq/B = 2.89 and C = 2036 cm⁻¹. The near-infrared luminescence centered at 1250 nm was not detected in the deep pink glass-ceramics unlike emerald green glass.     

Fluorinated silica glass ablated with ArF excimer laser at low fluence

Amorphous SiO₂ (a-SiO₂) was formed by liquid-phase deposition (LPD) at room temperature. As a result of one shot of ArF excimer laser irradiation, LPD-formed a-SiO₂ shows a threshold fluence for ablation of below than 200 mJ/cm², which is much lower than the threshold fluence (∼1 J/cm²) of a-SiO₂ formed by thermal oxidation of silicon. Raman scattering spectroscopy revealed that two sharp lines at 495 cm⁻¹ and 606 cm⁻¹, respectively, labeled D₁ and D₂, had disappeared, and the main band at 430 cm⁻¹ was sharpened in LPD-formed a-SiO₂. It is presumed that the fluorine broke the silica network, relaxing the Si-O-Si bond angle and dramatically reducing the threshold energy for ablation of a-SiO₂.     

Growth and property of Zn-doped near-stoichiometric LiTaO3 crystal

Near-stoichiometric LiTaO₃ (SLT) and Zn-doped near-stoichiometric LiTaO₃ (Zn:SLT) crystals with 10–15 mm in diameter and 10 mm in length were grown by using TSSG technique with K₂O as the flux. The effect of adding amount of K₂O was discussed in the growing process. The crystals were characterized by inductively coupled plasma-optical emission (ICP-OES), X-ray diffraction (XRD) and differential thermal analysis (DTA). The lattice constants of Zn:SLT were smaller than those of SLT and Curie temperature was higher than that of SLT. It was found that Zn doping is an efficient way to improve the optical damage resistance ability of SLT crystal. Compared with SLT crystal, Zn:SLT exhibited a much higher optical damage threshold, more than 500 MW/cm², which was attributed to Zn self-compensated effect that formed the charge compensated complexes, (Zn_Ta)³⁻–3(Zn_Li)⁺ in SLT crystal.     

Crystal growth and spectroscopic properties of erbium doped Lu2SiO5

A high optical quality erbium doped Lu₂SiO₅ single crystal has been grown by the Czochralski method. The distribution coefficient of Er³⁺ was measured to be ∼0.926. The absorption and emission spectra as well as the fluorescence decay curve of the excited state ⁴I_13/2 were measured at room temperature. The spectroscopic parameters were calculated using the Judd–Ofelt theory, and the J–O parameters Ω₂, Ω₄ and Ω₆ were found to be 4.451×10^-20, 1.614×10^-20 and 1.158×10^-20 cm², respectively. The room-temperature fluorescence lifetime of the Er³⁺⁴I_13/2→⁴I_15/2 transition was measured to be 7.74 ms. The absorption and emission cross-section as well as the gain cross-section in the eye-safe regime of 1400–1700 nm were also determined and discussed.     

Properties of gallium- and aluminum-doped bulk ZnO obtained from single-crystals grown by liquid phase epitaxy

Bulk properties of gallium (Ga)- and aluminum (Al)-doped zinc oxide (ZnO) were studied using bulky single-crystalline thick films grown by liquid phase epitaxy (LPE). The highest possible dopant concentration was 1×10¹⁹ cm^–3 for LPE growth at around 800 °C. The electron concentration was nearly same to the Ga and Al concentrations. The donor binding energy decreased to nearly zero with an increase in dopant concentration, and electron mobility of the sample with relatively high dopant concentration (1×10¹⁹ cm^–3) was more than 60 cm² V^–1 s^–1 at room temperature. The LPE technique is a potential solution for the production of ZnO for optical applications because the well-defined excitonic luminescence could be seen from the LPE-grown-doped single-crystals.     

Characterization of a newly synthesized organic nonlinear optical crystal: Urea ninhydrin monohydrate

Urea ninhydrin monohydrate (UNM) was synthesized and grown for the first time from aqueous solution employing the slow evaporation method. Single crystal structure was determined by X-ray diffraction data and it reveals that the crystal belongs to centrosymmetric with space group of P2₁/c. The grown crystals were characterized by thermogravimetric analysis (TGA), differential thermal analysis (DTA) and UV–vis–NIR spectroscopy. Preliminary Z-scan measurement indicates that nonlinear refractive index of this crystal is −4.1×10⁻⁸ cm²/W. The etching study was performed to assess the growth pattern of the crystal. Dielectric response of the crystal was analyzed for different frequencies and temperatures.     

Droplet epitaxy of zinc-blende GaN quantum dots

Zinc-blende GaN quantum dots were grown on 3C-AlN(0 0 1) by a vapor–liquid–solid process in a molecular beam epitaxy system. We were able to control the density of the quantum dots in a range of 5×10⁸–5×10¹² cm⁻². Photoluminescence spectroscopy confirmed the optical activity of the GaN quantum dots in a range of 10¹¹–5×10¹² cm⁻². The data obtained give an insight to the condensation mechanism of the vapor–liquid–solid process in general, because the GaN quantum dots condense in metastable zinc-blende crystal structure supplied by the substrate, and not in the wurtzite crystal structure expected from free condensation in the droplet.     

The effect of composition on UV-vis-NIR spectra of iron doped glasses in the systems Na2O/MgO/SiO2 and Na2O/MgO/Al2O3/SiO2

Glasses with the compositions xNa₂O · 10MgO · (90 − x)SiO₂, 10Na₂O · xMgO · (90 − x)SiO₂, 5Na₂O · 15MgO · xAl₂O₃ · (80 − x)SiO₂, xNa₂O · 10MgO · 10Al₂O₃ · (80 − x)SiO₂, 10Na₂O · 10MgO · xAl₂O₃ · (80 − x)SiO₂, 10Na₂O · 5MgO · 10Al₂O₃ · (80 − x)SiO₂ were melted and studied using UV-vis-NIR spectroscopy in the wavenumber range from 5000 to 30 000 cm⁻¹. At [Al₂O₃] > [Na₂O], the UV-cut off is strongly shifted to smaller wavenumbers and the NIR peak at around 10 000 cm⁻¹ attributed to Fe²⁺ in sixfold coordination gets narrower. Furthermore, the intensity of the NIR peak at 5500 cm⁻¹ increases. This is explained by the incorporation of iron in the respective glass structures.     

Structural,electrical and optical properties of SnO2 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

SnO₂ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates at different substrate temperatures (500–800 °C) by metalorganic chemical vapor deposition (MOCVD). Structural, electrical and optical properties of the films have been investigated. The films deposited at 500 and 600 °C are epitaxial SnO₂ films with orthorhombic columbite structure, and the HRTEM analysis shows a clear epitaxial relationship of columbite SnO₂(1 0 0)||YSZ(1 0 0). The films deposited at 700 and 800 °C have mixed-phase structures of rutile and columbite SnO₂. The carrier concentration of the films is in the range from 1.15×10¹⁹ to 2.68×10¹⁹ cm⁻³, and the resistivity is from 2.48×10⁻² to 1.16×10⁻² Ω cm. The absolute average transmittance of the films in the visible range exceeds 90%. The band gap of the obtained SnO₂ films is about 3.75–3.87 eV.     

Iron redox equilibrium, structure and properties of zinc iron phosphate glasses

Iron redox equilibrium, structure and properties were investigated for the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glasses melted at different temperatures. The structure and valence states of the iron ions in these glasses were investigated using Mössbauer spectroscopy, Raman spectroscopy and differential thermal analysis. Mössbauer spectroscopy indicated that the concentration of Fe²⁺ ions increased in the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glass with increasing melting temperature. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio increased from 0.18 to 0.38 as the melting temperature increased from 1100 to 1300 °C. The measured isomer shifts showed that both Fe²⁺ and Fe³⁺ ions are in octahedral coordination. It was shown that the dc conductivity strongly depended on Fe²⁺/(Fe²⁺ + Fe³⁺) ratio in glasses. The dc conductivity increases with the increasing Fe²⁺ ion content in these glasses. The conductivity arises from the polaron hopping between Fe²⁺ and Fe³⁺ ions which suggests that the conduction is electronic in nature in zinc iron phosphate glasses.     

Microstructure and dielectric properties of La2O3 films prepared by ion beam assistant electron-beam evaporation

Ultrathin La₂O₃ gate dielectric films were prepared on Si substrate by ion assistant electron-beam evaporation. The growth processing, interfacial structure and electrical properties were investigated by various techniques. From XRD results, we found that the La₂O₃ films maintained the amorphous state up to a high annealing temperature of 900 °C for 5 min. From XPS results, we also discovered that the La atoms of the La₂O₃ films did not react with silicon substrate to form any La-compound at the interfacial layer. However, a SiO₂ interfacial layer was formed by the diffusion of O atoms of the La₂O₃ films to the silicon substrate. From the atomic force microscopy image, we disclosed that the surface of the amorphous La₂O₃ film was very flat. Moreover, the La₂O₃ film showed a dielectric constant of 15.5 at 1 MHz, and the leakage current density of the La₂O₃ film was 7.56 × 10⁻⁶ A/cm² at a gate bias voltage of 1 V.     

Reduction of the dislocation density in molecular beam epitaxial CdTe(2 1 1)B on Ge(2 1 1)

The high dislocation density (2×10⁷/cm² for a thickness of 7 μm) in CdTe(2 1 1)B on Ge(2 1 1) has become a roadblock for the technological exploitation of this material. We present a systematic study of in situ and post-growth annealing cycles aimed at reducing it. An etch pit density of 2×10⁶/cm² was achieved by optimizing the growth conditions and annealing the samples in situ. This finding was corroborated by high-resolution X-ray diffraction, atomic force microscopy, photoluminescence and ellipsometry measurements.     

Preparation and optical properties of samarium doped sol-gel materials

Transparent crack-free glassy monoliths containing up to 0.2 Sm/Si are prepared at room temperature by sol-gel technique. The sol-gel preparation conditions are: acid catalyzed hydrolysis followed by basic catalyzed gelation and controlled drying. The prepared xerogels are characterized by X-ray diffraction, thermogravimetry with Fourier transforming infrared spectroscopy, scanning electron microscopy and optical spectroscopy. The values of the phenomenological Ω-intensity parameters of Sm(III) ions in the gels are (in 10⁻²⁰ cm²) Ω₂ = 76 ± 16.71, Ω₄ = 3.01 ± 0.21, Ω₆ = 2.99 ± 0.41. The oscillator strengths of the Sm(III) ions in the gels are calculated. The results show a linear concentration dependence of Sm(III) in UV/Vis absorption spectra and formation of a Sm(NO₃)₃ · 6H₂O complex at high samarium concentrations.     

Growth and spectroscopic characteristics of Er:YbVO4 crystal

A laser crystal Er³⁺:YbVO₄ has been grown by the Czochralski method with excellent quality. The rocking curve from the (0 0 4) diffraction plane of the as-grown Er³⁺:YbVO₄ crystal was measured and the full-width at half-maximum value was found to be 19.80 in. for the (0 0 4) face. The effective segregation coefficient of Er³⁺ was studied by X-ray fluorescence and the crystal structure was determined by means of X-ray diffraction analysis. The polarized absorption spectra and the fluorescence spectra of Er³⁺:YbVO₄ were measured at room temperature. The spectral parameters were calculated based on the Judd–Ofelt theory, and the intensity parameters Ω₂, Ω₄ and Ω₆ are found to be 5.50×10⁻²⁰, 1.96×10⁻²⁰ and 2.34×10⁻²⁰ cm², respectively. The emission cross-section has been calculated by the Fuechtbauer–Ladenbury method. The spectroscopic parameters of Er³⁺:YbVO₄ are compared with other typical laser hosts.     

Assessment of defect reduction methods for nonpolar a-plane GaN grown on r-plane sapphire

This work assesses the relative effectiveness of four techniques to reduce the defect density in heteroepitaxial nonpolar a-plane GaN films grown on r-plane sapphire by metalorganic vapour phase epitaxy (MOVPE). The defect reduction techniques studied were: 3D–2D growth, SiN_x interlayers, ScN interlayers and epitaxial lateral overgrowth (ELOG). Plan-view transmission electron microscopy (TEM) showed that the GaN layer grown in a 2D fashion had a dislocation and basal-plane stacking fault (BSF) density of (1.9±0.2)×10¹¹ cm⁻² and (1.1±0.9)×10⁶ cm⁻¹, respectively. The dislocation and BSF densities were reduced by all methods compared to this 2D-grown layer (used as a seed layer for the interlayer and ELOG methods). The greatest reduction was achieved in the (0 0 0 1) wing of the ELOG sample, where the dislocation density was <1×10⁶ cm⁻² and BSF density was (2.0±0.7)×10⁴ cm⁻¹. Of the in-situ techniques, SiN_x interlayers were most effective: the interlayer with the highest surface coverage that was studied reduced the BSF density to (4.0±0.2)×10⁵ cm⁻¹ and the dislocation density was lowered by over two orders of magnitude to (3.5±0.2)×10⁸ cm⁻².     

Effect of electron irradiation on Na-K silicate glass investigated using X-ray photoelectron spectroscopy and pattern recognition method

Alkali silicate glasses and melts play an important role in material science. Electron interaction with glasses is important for radioactive waste deposition, where electrons of various energies lead to irreversible changes. These changes are caused mainly by ionization and ballistic interaction of electrons with atoms, introducing structural disorder, changes in atomic composition and chemical state, accompanied by alkali ions diffusion. The Na-K silicate glass (5Na₂O · 10K₂O · 85SiO₂), pristine and electron irradiated (doses from 25 C m⁻² to 20 236 C m⁻²) are investigated using X-ray photoelectron spectroscopy (XPS) and the pattern recognition (PR) and fitting procedures. Changes of composition and chemical state of atoms dependent on electron dose are analyzed. At low doses (100-300 C m⁻²), decrease followed by increase of O and Si concentrations was observed. Surface segregation, probable desorption, and in-bulk diffusion of K and Na ions (doses of about 50 C m⁻² and 2000 C m⁻², respectively) were observed. This was accompanied by changes in the chemical state of K atom, where with an electron dose increasing content of elemental K form accompanied by decreasing potassium peroxide form were observed. No difference in chemical state of Si and O atoms was visible under electron irradiation dose to 20 236 C m⁻², within the sensitivity of the applied method.     

Spectroscopic properties of Er-doped Na2O-Sb2O3-B2O3-SiO2 glasses

Spectroscopic properties of Er³⁺-doped Na₂O-Sb₂O₃-B₂O₃-SiO₂ glasses have been investigated for developing 1.5-μm broadband fiber amplifiers. An intense 1.5-μm near infrared emission with a broad full width at half maximum (FWHM) of 88 nm has been obtained for Er³⁺-doped 5Na₂O-20Sb₂O₃-35B₂O₃-40SiO₂ glass upon excitation with a 980 nm laser diode. The obtained emission cross-section of the ⁴I_13/2 → ⁴I_15/2 transition and the lifetime of the ⁴I_13/2 level of Er³⁺ ions are 6.8 × 10⁻²¹ cm² and 0.36 ms, respectively. It is noted that the product of the emission cross-section and the FWHM of the glass, σ_e × FWHM, is as great as 598.4 × 10⁻²¹ cm² nm, which is comparable or higher than that of Er³⁺-doped bismuth-based and tellurite-based glasses. These special optical properties encourage in identifying them as important materials for potential applications in high performance optics and optical communication networks.