High-resolution FTIR measurement of the ν4 band of methylene fluoride-d2

A high-resolution (0.002 cm⁻¹) infrared absorption spectrum of methylene fluoride-d₂ (CD₂F₂) of the lowest fundamental mode ν₄ in the region from 460 to 610 cm⁻¹ has been measured on a Bruker IFS 120-HR Fourier transform infrared spectrometer. More than 3500 transitions have been assigned in this B-type band centered at 521.9 cm⁻¹. The data have been combined with upper state pure rotational measurements in a weighted least-squares fit to obtain molecular constants for the upper state resulting in an overall standard deviation of 0.00018 cm⁻¹. Accurate value for the band origin (521.9578036 cm⁻¹) has been obtained and inclusion of transitions with very high J (?60) and K_a (?34) values has resulted in improved precision for sextic centrifugal distortion constants, in particular D_K, H_KJ, and H_K.     

Bulk vs. surface effects in ARPES experiment from La2/3Sr1/3MnO3 thin films

Experiments directly probing the electronic states using angle-resolved photoemission (ARPES) were carried out on La_2/3Sr_1/3MnO₃ in order to elucidate its electronic properties. ARPES is a surface sensitive technique where bulk and surface states are usually both present. We present high-resolution ARPES studies in the (1 0 0) and (1 1 0) mirror planes and compare them with simulated ARPES based on GGA + U band structure calculations. In the (1 1 0) mirror plane we identify surface umklapps accounted by surface reconstruction which couple to bulk electronic states. As predicted by the simulated spectra there is additional spectral intensity at the Fermi level detected in ARPES data due to k_⊥-broadening effects in the photoemission final states. We demonstrate that this additional spectral intensity is a convenient spectral marker for determination of the k_F Fermi momenta.     

Investigation on spectral features of tungsten ions in PbO-Bi2O3-As2O3 glass matrix

Lead bismuth arsenate glasses mixed with different concentrations of WO₃ (ranging from 0 to 6.0 mol%) were synthesized. Differential thermal analysis (DTA), optical absorption, ESR and IR spectral studies have been carried out. The results of DTA have indicated that there is a gradual decrease in the resistance of the glass against devitrification with increase in the concentration of WO₃ upto 4.0 mol%.The optical absorption spectra of these glasses exhibited a relatively broad band peaking at about 880 nm identified due to d_xy→d_x²_−y² transition of W⁵⁺ ions; this band is observed to be more intense in the spectrum of glass containing 4.0 mol% of WO₃. Further, two prominent kinks attributed to ³P₀→¹S₀, ¹D₂ transitions of Bi³⁺ ions have also been located in the absorption spectra. The ESR spectra of these glasses recorded at room temperature exhibited an asymmetric signal at g_⊥∼1.71 and g_ll∼1.61. The intensity of the signal is observed to be maximal for the spectrum of the glass W₄. The quantitative analysis of optical absorption and ESR spectral studies have indicated that there is a maximum reduction of tungsten ions from W⁶⁺ state to W⁵⁺ state in the glass containing 4.0 mol% of WO₃. The IR spectral studies have indicated that there is a increasing degree of disorder in the glass network with increase in the concentration of WO₃ upto 4.0 mol%.     

The AB2-XA1 electronic transition of NO2: A rovibronic survey covering 14 300-18 000 cm

More than 250 rotationally resolved vibrational bands of the A²B₂-X²A₁ electronic transition of ¹⁵NO₂ have been observed in the 14 300-18 000 cm⁻¹ range. The bands have been recorded in a recently constructed setup designed for high resolution spectroscopy of jet cooled molecules by combining time gated fluorescence spectroscopy and molecular beam techniques. The majority of the observed bands has been rotationally assigned and can be identified as transitions starting from the vibrational ground state or from vibrationally excited (hot band) states. An exceptionally strong band is located at 14 851 cm⁻¹ and studied in more detail as a typical benchmark transition to monitor ¹⁵NO₂ in atmospheric remote sensing experiments. Standard rotational fit routines provide band origins, rotational and spin rotation constants. A subset of 177 vibronic levels of ²B₂ vibronic symmetry has been analyzed in the energy range between 14 300 and 17 250 cm⁻¹, in terms of integrated density and using Next Neighbor Distribution. It is found that the overall statistical properties and polyad structure of ¹⁵NO₂ are comparable to those of ¹⁴NO₂ but that the internal structures of the polyads are completely different. This is a direct consequence of the X²A₁-A²B₂ vibronic mixing.     

On the ferromagnetism of AlFe2B2

Based on extensive Mossbauer effect (ME) and magnetization measurements, the orthorhombic AlFe₂B₂ was characterized as a ferromagnet (FM) because this character is evident as an onset of a FM transition at T_c=320 K and characteristic magnetizations isotherms below T_c. At liquid helium temperatures, the magnetization saturates to μ_sat≈1μ_B per Fe atom; a value which is half the one reported for the iron metal indicating a relatively more filled 3d band. The ME analysis revealed a hyperfine field H(0) of 88(2) kOe, an isomer shift (relative to Fe) of 0.50(2) mm/s, and a quadrupole parameter of 0.02 mm/s: all parameters extrapolated to zero Kelvin. The itinerant character of the magnetic moment will be discussed.     

High-resolution FTIR spectroscopy of the 3ν2 band of PH3

High-resolution Fourier transform spectrum of phosphine (PH₃) at room temperature has been recorded in the region of the 3ν₂ band (2730-3100 cm⁻¹) at an apodized resolution of 0.005 cm⁻¹. About 200 vibration-rotation transitions have been least squares fitted with an rms of 0.00039 cm⁻¹ after taking into account the ΔK = ±3 interaction.     

Rotational spectrum and structure of asymmetric dinitrogen trioxide, N2O3

The rotational spectra of the ground vibrational state and the ν₉ = 1 torsional state have been reinvestigated and accurate spectroscopic constants have been determined. The torsional frequency, ν₉ = 70(15) cm⁻¹, has been determined by relative intensity measurements. The assignment of the infrared spectrum has been slightly revised and an accurate harmonic force field has been calculated. The equilibrium structure has been determined using different, complementary methods: experimental, semi-experimental and ab initio, leading to r(NN) = 1.870(2) Å, in particular.     

Effect of concentration on the luminescence of Eu ions in nanocrystalline La2O3

Nanocrystalline powders with various Eu³⁺ concentration (from 1 to 10 mol %) doped La₂O₃ were prepared via a combustion route. Their structure and morphology were characterized using X-ray diffraction (XRD) and High-resolution transmission electron microscopy. The emission spectra of the as-synthesized samples show that the strongest emission position is centered at 626 nm corresponding to ⁵D₀→⁷F₂ transition of Eu³⁺ ions and the intensity change of 626 nm emission is considered as a function of ultraviolet (240 nm) irradiation time. The excitation spectra at 626 nm monitoring indicate that the charge transfer state band is varies with different Eu³⁺ ion concentration. These results are attributed to the surface defects of the nanocrystals.     

Observation of the K2 4Δg state by cw perturbation-facilitated optical-optical double resonance spectroscopy

This paper reports for the first time both, an experimental observation and theoretical calculations of the K₂ 4³Δ_g state. For the experiment we used cw perturbation-facilitated optical-optical double resonance (PFOODR) spectroscopy. A single mode Ti-sapphire laser and a dye laser served as the pump and probe lasers, respectively. A total of 55 PFOODR signals have been assigned to the 4³Δ_g ← b³Π_u transitions. Absolute vibrational numbering was determined by using quantum defect analysis combined with comparing observed intensities with calculated Franck-Condon factors (FCF). For the former we used known parameters from the 2³Δ_g state since the 2³Δ_g and the 4³Δ_g states belong to the same Rydberg series. We report here our experimental and calculated spectroscopic constants, the corresponding RKR potential energy curve, the Franck-Condon table for the 4³Δ_g ↔ b³ Π_u system, as well as a comparison with the theoretical potential energy curve. The T_e value is found to be 28408.938(52) cm⁻¹.     

Iron isotope effect on Tc in optimally-doped (Ba,K)Fe2As2 (Tc = 38 K) and SmFeAsO1−y (Tc = 54 K) superconductors

We report the iron isotope effect on a transition temperature (T_c) in an optimally-doped (Ba,K)Fe₂As₂ (T_c = 38 K) and SmFeAsO_1−y (T_c = 54 K) superconductors. In order to obtain the reliable isotope shift in T_c, twin samples with different iron isotope mass are synthesized in the same conditions (simultaneously) under high-pressure. We have found that (Ba,K)Fe₂As₂ shows an inverse iron isotope effect α_Fe = −0.18 ± 0.03 while SmFeAsO_1−y shows a small iron isotope effect α_Fe = −0.02 ± 0.01, where the isotope exponent α is defined by T_c ∼ M^−α (M is the isotopic mass). The results show that α_Fe changes in the iron-based superconductors depending on the system. The distinct iron isotope effects imply the exotic coupling mechanism in the iron-based superconductors.     

Dry etching of CuCrO2 thin films

Highly conducting films of p-type CuCrO₂ are attractive as hole-injectors in oxide-based light emitters. In this paper, we report on the development of dry etch patterning of CuCrO₂ thin films. The only plasma chemistry that provided some chemical enhancement was Cl₂/Ar under inductively coupled plasma conditions. Etch rates of ∼500 Å min⁻¹ were obtained at chuck voltages around −300 V and moderate source powers. In all cases, the etched surface morphologies were improved relative to un-etched control samples due to the smoothing effect of the physical component of the etching. The threshold ion energy for the onset of etching was determined to be 34 eV. Very low concentrations (≤1 at.%) of residual chlorine were detected on the etched surfaces but could be removed by simple water rinsing.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

Diode laser absorption spectrum of cold bands of C2HD at 6500 cm

The absorption spectrum of acetylene-d has been observed at high resolution between 6470 and 6630 cm⁻¹ using an external cavity diode laser. Three cold bands have been observed: the strong 2ν₁ band, the weaker ν₁ + ν₂ + 2ν₅ band, and the (ν₁ + ν₃ + ν₅)¹ band, which gains its intensity through Coriolis resonance with 2ν₁. Centers of unblended lines are determined with an accuracy of approximately 10 MHz.     

Gas phase electronic spectrum of propadienylidene C3H2

The rotationally resolved vibronic bands in the forbidden electronic transition of the cumulene carbene C₃H₂ have been observed in the gas phase by cavity ring down absorption spectroscopy through a supersonic planar plasma with allene as precursor. The band detected in the 16 223 cm⁻¹ region is a result of vibronic interaction and is assigned to a combination of a₁ and b₂ vibrations with a frequency around 2250 cm⁻¹. Another vibronic band near 15 810 cm⁻¹ has an unusual rotational structure because the K_a = 0-1 subband is absent. It is assigned to a combination of a₁ and b₁ vibrations, ∼1850 cm⁻¹, which borrow intensity from the near lying state due to a-type Coriolis coupling. A rotational analysis using a conventional Hamiltonian for an asymmetric top molecule yields molecular constants for the vibrational excited levels of the ùA₂ state, which were used for the determination of the geometry. The stronger transition of C₃H₂, measured in a neon matrix in the 16 161-24 802 cm⁻¹ range, was not detected. The reason for this is a short lifetime of the state, leading to line broadening.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Chemical quenching of positronium in Fe2O3/Al2O3 catalysts

Fe₂O₃/Al₂O₃ catalysts were prepared by solid state reaction method using α-Fe₂O₃ and γ-Al₂O₃ nano powders. The microstructure and surface properties of the catalyst were studied using positron lifetime and coincidence Doppler broadening annihilation radiation measurements. The positron lifetime spectrum shows four components. The two long lifetimes τ₃ and τ₄ are attributed to positronium annihilation in two types of pores distributed inside Al₂O₃ grain and between the grains, respectively. With increasing Fe₂O₃ content from 3 wt% to 40 wt%, the lifetime τ₃ keeps nearly unchanged, while the longest lifetime τ₄ shows decrease from 96 ns to 64 ns. Its intensity decreases drastically from 24% to less than 8%. The Doppler broadening S parameter shows also a continuous decrease. Further analysis of the Doppler broadening spectra reveals a decrease in the p-Ps intensity with increasing Fe₂O₃ content, which rules out the possibility of spin-conversion of positronium. Therefore the decrease of τ₄ is most probably due to the chemical quenching reaction of positronium with Fe ions on the surface of the large pores.     

Hydrostatic pressure study of the structural phase transitions and superconductivity in single crystals of (Ba1−xKx)Fe2As2 (x=0 and 0.45) and CaFe2As2

We studied the effect of hydrostatic pressure (P) on the structural phase transitions and superconductivity in the ternary and pseudo-ternary iron arsenides CaFe₂As₂, BaFe₂As₂, and (Ba_0.55K_0.45)Fe₂As₂, by means of measurements of electrical resistivity (ρ) in the 1.8-300 K temperature (T) range, pressures up to 20 kbar, and magnetic fields up to 9 T. CaFe₂As₂ and BaFe₂As₂ (lightly doped with Sn) display structural phase transitions near 170 and 85 K, respectively, and do not exhibit superconductivity in ambient pressure, while K-doped (Ba_0.55K_0.45)Fe₂As₂ is superconducting for T<30 K. The effect of pressure on BaFe₂As₂ is to shift the onset of the crystallographic transformation down in temperature at the rate of ~−1.04 K/kbar, while shifting the whole ρ(T) curves downward, whereas its effect on superconducting (Ba_0.55K_0.45)Fe₂As₂ is to shift the onset of superconductivity to lower temperatures at the rate of ~−0.21 K/kbar. The effect of pressure on CaFe₂As₂ is first to suppress the crystallographic transformation and induce superconductivity with onset near 12 K very rapidly, i.e., for P<5 kbar. However, higher pressures bring about another phase transformation characterized by reduced-resistivity, and the suppression of superconductivity, confining superconductivity to a narrow pressure dome centered near 5 kbar. Upper critical field (H_c2) data in (Ba_0.55K_0.45)Fe₂As₂ and CaFe₂As₂ are discussed.     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

A new self-activated yellow-emitting phosphor Zn2V2O7 for white LED

A new self-activated yellow-emitting Zn₂V₂O₇ phosphor was synthesized by high temperature solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the sample with monoclinic formation of Zn₂V₂O₇. The excitation and emission spectra indicated the phosphor can be efficiently excited by near ultraviolet (NUV) light in 220–400 nm range and exhibit a bright broad yellow emission with the highest emission intensity at 531 nm. The broad emission band from 400 to 650 nm can be attributed to the charge transfer transition in the VO₄ tetrahedra, which suggests that the phosphor is a promising yellow phosphor applied for white light-emitting diodes (WLED).     

Absorption spectrum of nitrous acid for the ν1+2ν3 band studied with continuous-wave cavity ring-down spectroscopy and theoretical calculations

We present the high resolution absorption measurements of gaseous HONO at room temperature using continuous-wave cavity ring-down spectroscopy in the near-infrared region between 6017 and 6067 cm⁻¹ at a resolution of 1 pm (0.037 cm⁻¹). For the trans-HONO isomer an extensive analysis of the ν₁+2ν₃ combination band 6045.8089 cm^-1 was performed starting from the results of a previous study for the 1¹ and 3¹ vibrational states [Guilmot J-M, Godefroid M, Herman M. Rovibrational parameters for trans-nitrous acid. J Mol Spectrosc 1993;160:387-400]. The present combination band is perturbed because of the existence of several dark states of HONO which could not be identified unambiguously. The rotational constants achieved for the 1¹3² state deviate slightly from the values which are predicted from the rotational constants achieved in the previous studies for the 1¹ and 3¹ vibrational states of trans-HONO.