A tunable green alkaline-earth silicon-oxynitride solid solution (Ca1? x Sr x )Si2O2N2:Eu2+ and its application in LED

A series of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ (x=0.0–0.97, y=0.03) phosphors were synthesized by high-temperature solid-state reaction. The XRD patterns confirm the formation of a solid solution of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺. An intense tunable green light is observed with the increasing ratio of Sr/Ca. With an increase in x, the excitation and emission spectra show a redshift and blueshift, respectively, due to large centroid shift and small Stokes shift. The temperature dependent luminescence is also investigated in the temperature range of 77–450 K. The Huang–Rhys factor and the thermal-quenching temperature are determined. Intense green LEDs were successfully fabricated based on the (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ phosphor and near-ultraviolet (∼395 nm) GaN/blue (460 nm) InGaN chips. All the results indicate that the solid solution (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ is a promising phosphor applicable to near-UV and blue LEDs for solid-state lighting.     

Pulsed laser deposition of Zr–N codoped <Emphasis Type="Italic">p</Emphasis>-type ZnO thin films

Present p-type ZnO films tend to exhibit high resistivity and low carrier concentration, and they revert to their natural n-type state within days after deposition. One approach to grow higher quality p-type ZnO is by codoping the ZnO during growth. This article describes recent results from the growth and characterization of Zr–N codoped p-type ZnO thin films by pulsed laser deposition (PLD) on (0001) sapphire substrates. For this work, both N-doped and Zr–N codoped p-type ZnO films were grown for comparison purposes at substrate temperatures ranging between 400 to 700 °C and N₂O background pressures between 10⁻⁵ to 10⁻² Torr. The carrier type and conduction were found to be very sensitive to substrate temperature and N₂O deposition pressure. P-type conduction was observed for films grown at pressures between 10⁻³ to 10⁻² Torr. The Zr–N codoped ZnO films grown at 550 °C in 1×10⁻³ Torr of N₂O show p-type conduction behavior with a very low resistivity of 0.89 Ω-cm, a carrier concentration of 5.0×10¹⁸ cm⁻³, and a Hall mobility of 1.4 cm² V⁻¹ s⁻¹. The structure, morphology and optical properties were also evaluated for both N-doped and Zr–N codoped ZnO films.     

Ferroelectric phase stabilization, phase transformations and?thermal properties in (1? x )PbZrO3– x Pb(Co1/3Nb2/3)O3 solid solution

The solid solution between the antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Co_1/3Nb_2/3)O₃ (PCoN) was synthesized by the columbite method. The phase structure and thermal properties of (1−x)PZ–xPCoN, where x=0.0–0.3, were investigated. With these data, the ferroelectric phase diagram between PZ and PCoN has been established. The crystal structure data obtained from XRD indicates that the solid solution PZ–PCoN, where x=0.0–0.3, successively transforms from orthorhombic to rhombohedral symmetry with an increase in PCoN concentration. The AFE→FE phase transition was found in the compositions of 0.0≤x≤0.10. The AFE→FE phase transition shift to lower temperatures with higher compositions of x. The width of the temperature range of FE phase was increased with increasing amount of PCoN. It is apparent that the replacement of the Zr⁴⁺ ion by (Co_1/3Nb_2/3)⁴⁺ ions would decrease the driving force for antiparallel shift of Pb²⁺ ions, because they interrupt the translational symmetry. This interruption caused the appearance of a rhombohedral ferroelectric phase when the amount of PCoN was more than 10 mol%.     

Azobenzene-functionalized alkanethiols in self-assembled monolayers on gold

Self-assembled monolayers (SAMs) of 4-trifluoromethyl-azobenzene-4′-methyleneoxy-alkanethiols (CF₃– C₆H₄–N=N–C₆H₄–O–(CH₂) _n –SH on (111)-oriented poly-crystalline gold films on mica were examined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The spectra are analyzed with the help of density-functional-theory calculations of the isolated molecule. Only one doublet is detected in the sulphur 2p spectra of the investigated SAMs, consistent with a thiolate bond of the molecule to the gold surface. The C 1s XP spectra and the corresponding XAS π ^* resonance exhibit a rich structure which is assigned to the carbon atoms in the different chemical surroundings. Comparing XPS binding energies of the azobenzene moiety and calculated initial-state shifts reveals comparable screening of all C 1s core holes. While the carbon 1s XPS binding energy lies below the π ^*-resonance excitation-energy, the reversed order is found comparing core ionization and neutral core excitation of the nitrogen 1s core-hole of the azo group. This surprising difference in core-hole binding energies is interpreted as site-dependent polarization screening and charge transfer among the densely packed aromatic moieties. We propose that a quenching of the optical excitation within the molecular layer is thus one major reason for the low trans to cis photo-isomerization rate of azobenzene in aromatic-aliphatic SAMs.     

Facile synthesis and phase control of copper chalcogenides with different morphologies

A series of stoichiometric and nonstoichiometric copper–chalcogenide nanocrystallines with different morphologies, e.g., extremely high aspect ratio nanofibers (Cu₉S₈), tubular structure (Cu _x S (x=∼1.86–1.96), nanorods (CuS, Cu₃₁S₁₆), platelets (β-CuSe, Cu₃Se₂), rope-like Cu₃Se₂, as well as spherical nanoparticles (Cu₇Se₄, Cu_2−x Se), have been successfully synthesized in 20 vol% water and 80 vol% organic solvents mixture under mild conditions. The products were characterized by various techniques, including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), electronic diffraction (ED), and high-resolution transmission electron microscopy (HRTEM). The studies of the optical properties revealed that the copper chalcogenides have a wide absorption in the range of about 400–700 nm, with accessional IR band. Systematic studies showed that the mixture of 20 vol% water and 80 vol% organic solvents played a key role in controlling the copper chalcogenides with different morphologies and phases.     

Non-steady-state photo-EMF in nanostructured GaN and polypyrrole within porous matrices

We report an experimental investigation of the non-steady-state photoelectromotive force in nanostructured GaN within porous glass and polypyrrole within chrysotile asbestos. The samples are illuminated by an oscillating interference pattern created by two coherent light beams and the alternating current is detected as a response of the material. Dependences of the signal amplitude versus temporal and spatial frequencies, light intensity, and temperature are studied for two wavelengths λ=442 and 532 nm. The conductivity of the GaN composite is measured: σ=(1.1–1.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=442 nm, I ₀=0.045–0.19 W/cm², T=293 K) and σ=(3.5–4.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=532 nm, I ₀=2.3 W/cm², T=249–388 K). The diffusion length of photocarriers in polypyrrole nanowires is also estimated: L _D=0.18 μm.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

Sensitive detection of temperature behind reflected shock waves using wavelength modulation spectroscopy of CO2 near 2.7?μm

Tunable diode-laser absorption of CO₂ near 2.7 μm incorporating wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) is used to provide a new sensor for sensitive and accurate measurement of the temperature behind reflected shock waves in a shock-tube. The temperature is inferred from the ratio of 2f signals for two selected absorption transitions, at 3633.08 and 3645.56 cm⁻¹, belonging to the ν ₁+ν ₃ combination vibrational band of CO₂ near 2.7 μm. The modulation depths of 0.078 and 0.063 cm⁻¹ are optimized for the target conditions of the shock-heated gases (P∼1–2 atm, T∼800–1600 K). The sensor is designed to achieve a high sensitivity to the temperature and a low sensitivity to cold boundary-layer effects and any changes in gas pressure or composition. The fixed-wavelength WMS-2f sensor is tested for temperature and CO₂ concentration measurements in a heated static cell (600–1200 K) and in non-reactive shock-tube experiments (900–1700 K) using CO₂–Ar mixtures. The relatively large CO₂ absorption strength near 2.7 μm and the use of a WMS-2f strategy minimizes noise and enables measurements with lower concentration, higher accuracy, better sensitivity and improved signal-to-noise ratio (SNR) relative to earlier work, using transitions in the 1.5 and 2.0 μm CO₂ combination bands. The standard deviation of the measured temperature histories behind reflected shock waves is less than 0.5%. The temperature sensor is also demonstrated in reactive shock-tube experiments of n-heptane oxidation. Seeding of relatively inert CO₂ in the initial fuel-oxidizer mixture is utilized to enable measurements of the pre-ignition temperature profiles. To our knowledge, this work represents the first application of wavelength modulation spectroscopy to this new class of diode lasers near 2.7 μm.     

Impact of SOD-Mimetic Manganoporphyrins on Spin Trapping of Superoxide and Related Artifacts

The superoxide dismutase (SOD)-mimetic effectiveness of [meso-tetrakis(R)porphyrinato]manganese with R = 1,3-di-N-ethylimidazolium-2-yl (Mn-TDEIP), 1,3-di-N-methylimidazolium-2-yl (Mn-TDMIP), 1,3-di-N-propylimidazolium-2-yl (Mn-TDPIP), N-ethyl-2-pyridyl (Mn-T2EPyP), 4-sulphonatophenyl (Mn-TSP), 1-methyl-4-pyridyl (Mn-T4PyP), 4-carboxyphenyl (Mn-TBAP), and β-octabromo-meso-tetrakis(4-carboxyphenyl porphyrinato)manganese (MnBr₈TBAP) was compared with Cu, Zn SOD. Superoxide generated by reaction of xanthine oxidase with hypoxanthine was trapped with 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO), forming BMPO–OOH, which was monitored by electron paramagnetic resonance. Manganoporphyrins with redox potentials ranging from −0.190 to 0.346 V relative to the standard hydrogen electrode were selected for this study. With 0.1 μM manganoporphyrins and 20 mM BMPO, the effectiveness of the manganoporphyrins in inhibiting formation of BMPO–OOH increases in the order Mn-TSP < Mn-TBAP < MnBr₈TBAP < Mn-T4PyP < Mn-T2EPyP < Mn-TDEIP ~ Mn-TDMIP ~ Mn-TDPIP ~ Cu, Zn SOD. However, at higher concentrations of manganoporphyrin and BMPO, a BMPO–OH signal was observed. The formation of BMPO–OH was not inhibited by catalase or dimethylsulfoxide, which demonstrated that it was not produced from hydroxyl radical. The artifactual formation of BMPO–OH is attributed to oxidation of the water adduct of BMPO by the manganoporphyrins or decomposition of BMPO–OOH. Although spin trapping is an effective method for evaluating SOD-mimetic efficacy, caution must be exercised to ensure that artifact signals are not interpreted improperly.     

The Ag+ induced solution–liquid–solid growth, photoluminescence and photocatalytic activity of twinned ZnSe nanowires

Cubic ZnSe nanowires with periodically alternating twins along the wire growth direction are synthesized in the ZnCl₂–Na₂SeO₃–AgNO₃–ethylenediamine (EN)-ethylene glycol (EG)-polyvinyl–pyrrolidone (PVP) solvothermal system at 180°C for 12 h. The twinned ZnSe nanowires have diameters of 75±10 nm and lengths of >10 micrometers, and grow along 〈111〉 direction. The role of AgNO₃ in the formation of ZnSe nanowires was investigated, and an Ag⁺ induced solution–liquid–solid growth mechanism is also proposed to account for the conversion of microspheres assembled from ZnSe nanocrystallites into ZnSe nanowires. Compared with ZnSe microspheres, the as-prepared twinned ZnSe nanowires exhibit stronger band edge emissions of the wurtzite- and zinc-blende-structured ZnSe and lower deep defect related emission, and their photocatalytic ability is weaker than that of ZnSe microspheres. The results suggest that this simple, mild, one-step solution approach to fabricate ZnSe nanowires may be employed for the synthesis of other selenium compounds with one dimensional nanostructures, and provides opportunities for both fundamental research and technological applications.     

Nonlinear optical properties of antimony–germanium–sulfur glasses at 1560 nm

Nonlinear (NL) optical properties of antimony–germanium–sulfur (Sb–Ge–S) glasses were investigated using laser pulses of 65 fs at 1560 nm. Samples having concentration ratio [S]/[Ge]=2.69 with different antimony concentrations were studied. Glasses with different oxidation states of Sb were investigated using the thermally managed Z -scan technique. The influence of the Sb oxidation state on the NL properties was evaluated. NL refraction indices of electronic origin, n ₂≈10⁻¹³ cm²/W, two-orders of magnitude larger than for fused silica and NL absorption coefficients smaller than 0.55 cm/GW were measured. Appropriate figures-of-merit for photonic applications were determined.     

Preparation and characterization of graphitic carbon nitride through pyrolysis of melamine

Graphitic carbon nitride (g-C₃N₄) has been synthesized via a two-step pyrolysis of melamine (C₃H₆N₆) at 800°C for 2 h under vacuum conditions. X-ray diffraction (XRD) patterns strongly indicate that the synthesized sample is g-C₃N₄. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) morphologies indicate that the product is mainly composed of graphitic carbon nitride. The stoichiometric ratio of C:N is determined to be 0.72 by elemental analysis (EA). Chemical bonding of the sample has been investigated by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Electron energy loss spectroscopy (EELS) verifies the bonding state between carbon and nitrogen atoms. Optical properties of the g-C₃N₄ were investigated by PL (photoluminescence) measurements and UV–Vis (ultraviolet–visible) absorption spectra. We suppose its luminescent properties may have potential application as component of optical nanoscale devices. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were also performed.     

Properties of reactively sputtered W–B–N thin film as a diffusion barrier for Cu metallization on Si

Thin films of W–B–N (10 nm) have been evaluated as diffusion barriers for Cu interconnects. The amorphous W–B–N thin films were prepared at room temperature via reactive magnetron sputtering using a W₂B target at various N₂/(Ar + N₂) flow ratios. Cu diffusion tests were performed after in-situ deposition of 200 nm Cu. Thermal annealing of the barrier stacks was carried out in vacuum at elevated temperatures for one hour. X-ray diffraction patterns, sheet resistance measurement, cross-section transmission electron microscopy images, and energy-dispersive spectrometer scans on the samples annealed at 500°C revealed no Cu diffusion through the barrier. The results indicate that amorphous W–B–N is a promising low resistivity diffusion barrier material for copper interconnects.     

Magnetoelectric effect in laminates of polymer-based pseudo-1–3 (Tb0.3Dy0.7)0.5Pr0.5Fe1.55 composite and?0.3Pb(Mg1/3Nb2/3)O3–0.7PbTiO3 single crystal

We report an extrinsic magnetoelectric effect in composite laminates made by sandwiching one thickness-polarized 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN–PT) piezoelectric single crystal plate between two length-magnetized, polymer-based pseudo-1–3 (Tb_0.3Dy_0.7)_0.5Pr_0.5Fe_1.55 magnetostrictive composite plates. The laminates exhibit large magnetoelectric voltage coefficients (α _V ) of ∼0.17 V/Oe with a flat response for frequencies in excess of 40 kHz and of ∼2.97 V/Oe at the natural resonance frequency of ∼65 kHz. The distinct advantages of the laminates include high magnetic field sensitivity, low Joule heating loss, wide operating bandwidth, and low cost.     

Nonlinear refraction of silver nanowires from nanosecond to femtosecond laser excitation

In order to investigate the effect of pulse width and solvent on the nonlinear properties of metal nanostructures, silver nanowires were fabricated in a direct current electric field (DCEF) using a solid-state ionic method and characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The nonlinear refractive index (γ) of silver nanowires suspended in ethanol was measured using the Z-scan technique and laser radiation of various (femto-, pico-, and nanosecond) pulse durations. Experimental results indicated that silver nanowires have obvious positive refractive nonlinearities and γ (the Kerr-induced self-focusing) increases as the pulse duration increases from 7.4×10⁻⁸ cm²/GW at 110 fs to 1.6×10⁻⁴ cm²/GW at 8 ns, due to the additional influence of the atomic reorientational Kerr effect in the case of longer pulses. Due to the solvent dependence of the nonlinear behavior of the silver nanowires, the nonlinear absorption and refraction of silver nanowires suspended in de-ionized water are smaller than those of silver samples suspended in ethanol. The thermal nonlinearities are insignificant in our experimental conditions.     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

Ferroelectric and phase transition studies in cesium nitrate: poly(vinyl?alcohol)?composite films

The composite films of cesium nitrate (CsNO₃) and poly(vinyl alcohol) (PVA) with varying composition were prepared using the solvent cast method. The hysteresis loop characteristics show optimum remnant polarization (P _r ) of 2.75 μC/cm² at 50 wt.% composition. The field emission scanning electron microscope images show a nearly homogeneous distribution of CsNO₃ grains in the 50 wt.% composite film. The temperature dependence of the remnant polarization shows a diffused transition temperature range from the ferroelectric to the paraelectric phase and this has been attributed to the reduced enthalpy. The butterfly features of the dielectric constant–voltage (ε–V) characteristics have been attributed to polarization switching.     

Improved electrical properties of HfTiO/GeO x N y gate dielectric Ge MOS capacitors by using wet–NO Ge-surface pretreatment

Reactive cosputtering is employed to prepare high-permittivity HfTiO gate dielectric on n-Ge substrate. Effects of Ge-surface pretreatment on the interface and gate leakage properties of the dielectric are investigated. Excellent performances of Al/HfTiO/GeO _x N _y /n-Ge MOS capacitor with wet–NO surface pretreatment have been achieved with a interface-state density of 2.1×10¹¹ eV⁻¹ cm⁻², equivalent oxide charge of −7.67×10¹¹ cm⁻² and gate leakage current density of 4.97×10⁻⁵ A/cm² at V _g =1 V.     

Er<Superscript>3+</Superscript> as glass structure modifier of Ga–Ge–S chalcogenide system

Er³⁺ clustering phenomenon in Ga–Ge–S chalcogenide system is studied using Raman spectroscopy. The Raman spectra from 10 to 500 cm⁻¹ for glasses (100−y)[15Ga₂S₃–85GeS₂]–yEr₂S₃ (y=0.08−5.00 mol. %) have been analyzed. To reveal the influence of the chemical composition on the glass structure the intensity of the peak corresponding to Ge–Ge (Ga–Ga) homopolar bonds has been examined. The peak intensity increase with Er₂S₃ concentration change in the region 0<C(Er₂S₃)<2 mol. % has been interpreted in terms of the sulphur deficiency in the glass resulting in the formation of S₃Ge–GeS₃ (S₃Ga-GaS₃) structural units. The further increase in concentration beyond 2 mol. % reduces the sulphur deficiency, which can be attributed to the formation of the ternary compound Er₃GaS₆. The structural units Er₃GaS₆ contain a large mol. fraction of Er³⁺ or, in other words, Er³⁺ clusters. The data obtained from the low-frequency Raman spectra (boson band) indicate strong variations of the medium-range order (MRO) in the glasses induced by Er³⁺. The observed behavior of the MRO size (the correlation length) with increasing of Er₂S₃ concentration provides for additional evidence of the Er³⁺ clustering.