Preparation of highly c-axis-oriented Bi4Ti3O12 thin films and their crystallographic, dielectric and optical properties

Bismuth titanate (Bi₄Ti₃O₁₂) thin films with a high c-axis orientation up to 99% were prepared on (100)-oriented silicon wafers by r.f. planar magnetron sputtering using a Bi₂TiO₅ ceramic target at a substrate temperature of 600 °C. From the Auger electron spectroscopy depth profile of the film, there is no evidence of interdiffusion of a specific element between the film and the substrate. Relative dielectric constant of these films depends on film thickness. The behavior was explained assuming a low-dielectric-constant interface layer. Using this assumption, the relative dielectric constant of Bi₄Ti₃O₁₂ film was estimated to be approximately 140. This value is close to that along the c axis in a bulk form. The remanent polarization and the coercive field were 0.8 μC cm⁻² and 20 kV cm⁻¹, respectively.     

Influence of Si doping level on the Raman and IR reflectivity spectra and optical absorption spectrum of GaN

The optical absorption (hν) and Raman and Infra Red (IR) spectra of Si doped GaN layers deposited on sapphire through buffer layers have been recorded for electron concentrations from 5×10¹⁷ to 5×10¹⁹ cm⁻³. The (hν) values deduced from photothermal deflection spectroscopy (0.5–3.5 eV) and IR absorption (0.15–0.5 eV) vary between 50 and 10⁴ cm⁻¹ showing doping dependant free electron absorption at low energy, doping independant band gap at high energy, and slowly doping dependant defect absorption in the medium energy range. In our micro Raman geometry, maxima appear or can be deduced near the frequency expected for either the A₁(LO⁻) or the A₁(LO⁺) modes split from the A₁(LO) mode by plasmon phonon interaction. There is a large systematic evolution in the expected way for the IR reflectivity.     

Crystal growth and spectral properties of pure and Co-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

Excited-state absorption at 1.57 μm in U:CaF2 and Co:ZnSe saturable absorbers

Appreciable excited-state absorption (ESA) in U²⁺:CaF₂ and Co²⁺:ZnSe saturable absorbers was measured at λ=1.573 μm by optical transmission versus light fluence curves of 30–40 ns long pulses. The ground- and excited-state absorption cross-sections obtained were (9.15±0.3)×10⁻²⁰ and (3.6±0.2)×10⁻²⁰ cm², respectively, for U²⁺:CaF₂, and (57±4)×10⁻²⁰ and (12.5±1)×10⁻²⁰ cm² for Co²⁺:ZnSe. Thus, ESA is not negligible in U²⁺:CaF₂ and Co²⁺:ZnSe, as previously estimated.     

Luminosity monitor for the venus detector at TRISTAN

We constructed a luminosity monitor of the lead-scintillator sandwich type for the VENUS detector at the e⁺e⁻ collider TRISTAN. Photomultiplier tubes with transmissive mesh dynodes could be operated fairly well in a high magnetic field and hence the readout optics system was considerably simplified. We present the performance of the luminosity monitor for e⁺e⁻ collisions at √s = 50 and 52 GeV.     

Effect of silver addition on the properties of combustion synthesized nanocrystalline LiCoO2

Nanocrystalline (50 nm) LiCoO₂ powders containing 0–10 mol% of Ag have been prepared by combustion synthesis using citrate–nitrate combustion route. Thermal analyses show a sharp decomposition of the gel at 177 °C for pristine LiCoO₂. With addition of silver, the decomposition becomes sluggish and it completes only above 430 °C. X-ray powder diffraction analyses show an increase in lattice parameter, c, with increasing Ag content suggesting the occupation of Ag within LiCoO₂ interlayer spacings. Transmission electron microscopy indicates diffusion of Ag into LiCoO₂ grains. It has been observed that adding 1.0 mol% silver increases the room temperature electrical conductivity by more than two orders of magnitude (1.5 × 10⁻³ S cm⁻¹). Galvanostatic charge–discharge profiles of coin cells fabricated with the synthesized powders show a two-fold enhancement in the discharge capacity for 1.0 mol% Ag-added LiCoO₂ cathode (140 mAh g⁻¹) compared to that for pristine LiCoO₂ (70 mAh g⁻¹).     

Infrared absorption and Zeeman effect in Nd doped YVO4

Low temperature infrared transmission studies of Nd³⁺ doped YVO₄ were performed, under a magnetic field B c, in the 1800–8000 cm⁻¹ range of the ⁴I_9/2→⁴I_11/2, ⁴I_13/2, and ⁴I_15/2 Nd³⁺ crystal-field transitions. Good agreement is obtained between the experimental and calculated g-factors. Frequencies of the satellites in the ⁴I_9/2→⁴F_3/2 transitions of the Nd³⁺ isolated ion confirm the presence of ferromagnetic interactions between pairs of coupled Nd³⁺ ions that lift the Kramers doublet degeneracies of their ground state and excited multiplets.     

Dielectric properties of AlN films prepared by laser-induced chemical vapour deposition

The dielectric properties and electrical conductivity of AlN films deposited by laser-induced chemical vapour deposition (LCVD) are studied for a range of growth conditions. The static dielectric constant is 8.0 ± 0.2 over the frequency range 10²−10⁷ Hz and breakdown electric fields better than 10⁶ V cm⁻¹ are found for all films grown at temperatures above 130°C. The resistivity of the films grown under optimum conditions (substrate temperature above 170°C, NH₃/TMA flow rate ratio greater than 300 and a deposition pressure of 1–2 Torr) is about 10¹⁴ Ω cm and two conduction mechanisms can be identified. At low fields, F < 5 × 10⁵ V cm⁻¹ and conductivity is ohmic with a temperature dependence showing a thermal activation energy of 50–100 meV, compatible with the presumed shallow donor-like states. At high fields, F > 1 × 10⁶ V cm⁻¹, a Poole-Frenkel (field-induced emission) process dominates, with electrons activated from traps at about 0.7–1.2 eV below the conduction band edge. A trap in this depth region is well-known in AlN. At fields between 4 and 7 × 10⁵ V cm⁻¹ both conduction paths contribute significantly. The degradation of properties under non-ideal growth conditions of low temperature or low precursor V/III ratio is described.     

Tests of a silica aerogel Cherenkov counter

A Cherenkov counter with silica aerogel of refractive index 1.06 as radiator has been constructed and tested. The Cherenkov light produced in 9 cm thick silica aerogel was detected with four 5″-photomultipliers through a 162 cm long air light guide. The photoelectron yield for a 1 GeV/c pion beam was found to be 6 and uniform over a sensitive area of 40 × 30 cm².     

The CPLEAR electromagnetic calorimeter

A large-acceptance lead/gas sampling electromagnetic calorimeter (ECAL) was constructed for the CPLEAR experiment to detect photons from decays of π⁰s with momentum p_π⁰ ≤ 800 MeV/c. The main purpose of the ECAL is to determine the decay vertex of neutral-kaon decays K⁰ → π⁰π⁰ → 4γ and K⁰ → π⁰π⁰π⁰ → 6γ. This requires a position-sensitive photon detector with high spatial granularity in r−, −, and z−coordinates. The ECAL - a barrel without end-caps located inside a magnetic field of 0.44 T - consists of 18 identical concentric layers. Each layer of 1/3 radiation length (X₀) contains a converter plate followed by small cross-section high-gain tubes of 2640 mm active length which are sandwiched by passive pick-up strip plates. The ECAL, with a total of 6X₀ has an energy resolution of and a position resolution of 4.5 mm for the shower foot. The shower topology allows separation of electrons from pions. The design, construction, read-out electronics, and performance of the detector are described.     

Synthesis, structure refinement and characterization of tetrahydrated acid gadolinium diphosphate HGdP2O7·4H2O

Synthesis and single crystal structure are reported for a new gadolinium acid diphosphate tetrahydrate HGdP₂O₇·4H₂O. This salt crystallizes in the monoclinic system, space group P2₁/n, with the following unit-cell parameters: a = 6.6137(2) Å, b = 11.4954(4) Å, c = 11.377(4) Å, β = 87.53(2)° and Z = 4. Its crystal structure was refined to R = 0.0333 using 1783 reflections. The corresponding atomic arrangement can be described as an alternation of corrugated layers of monohydrogendiphosphate groups and GdO₈ polyhedra parallel to the () plane. The cohesion between the different diphosphoric groups is provided by strong hydrogen bonding involving the W4 water molecule.

IR and Raman spectra of HGdP₂O₇·4H₂O confirm the existence of the characteristic bands of diphosphate group in 980–700 cm⁻¹ area. The IR spectrum reveals also the characteristic bands of water molecules vibration (3600–3230 cm⁻¹) and acidic hydrogen ones (2340 cm⁻¹). TG and DTA investigations show that the dehydration of this salt occurs between 79 and 900 °C. It decomposes after dehydration into an amorphous phase. Gadolinium diphosphate Gd₄(P₂O₇)₃ was obtained by heating HGdP₂O₇·4H₂O in a static air furnace at 850 °C for 48 h.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Characterization of fluorine-doped silicon dioxide film by Raman spectroscopy

We have measured Raman spectra of fluorine-doped SiO₂ (SiOF) films and quartz glass. From a comparison between Raman spectra of the SiO₂ film and quartz glass, it has been found that the SiO₂ film is under compressive stress and that it has more threefold ring defects than quartz glass. Raman bands from threefold and fourfold ring defects in SiOF films become week as the fluorine/oxygen (F/O) ratio increases and as the stress decreases. The decrease of intensities of these Raman bands shows that ring defects in SiOF films decrease as the F/O ratio increases and as the stress decreases. The triply degenerated ω₄ mode at 460 cm⁻¹ becomes sharp as the F/O ratio increases and as the stress decreases. Furthermore, the peak-frequency of ω₁ mode around 820 cm⁻¹ decreases with a decrease of stresses whereas that of ω₃ mode around 1065 cm⁻¹ increases. These results can be well understood in terms of a decrease of O-Si-O bonding angle caused by relaxation of stresses.     

Optically active Er–Yb codoped Y2O3 films produced by pulsed laser deposition

Optically active Er³⁺:Yb³⁺ codoped Y₂O₃ films have been produced on c-cut sapphire substrates by pulsed laser deposition from ceramic Er:Yb:Y₂O₃ targets having different rare-earth concentrations. Stoichiometic films with very high rare-earth concentrations (up to 5.5 × 10²¹ at cm^− 3) have been achieved by using a low oxygen pressure (1 Pa) during deposition whereas higher pressures lead to films having excess of oxygen. The crystalline structure of such stoichiometric films was found to worsen the thicker the films are. Their luminescence at 1.53 μm and up-conversion effects have been studied by pumping the Yb³⁺ at 0.974 μm. The highest lifetime value (up to 4.6 ms) is achieved in films having Er concentrations of ≈ 3.5 × 10²⁰ at cm^− 3 and total rare-earth concentration ≈ 1.8 × 10²¹ at cm^− 3. All the stoichiometric films irrespective of their rare-earth concentration or crystalline quality have shown no significant up-conversion.     

The optical and electrical properties of copper indium di-selenide thin films

Thin films of copper indium di-selenide (CIS) with a wide range of compositions near stoichiometry have been formed on glass substrates in vacuum by the stacked elemental layer (SEL) deposition technique. The compositional and optical properties of the films have been measured by proton-induced X-ray emission (PIXE) and spectrophotometry (photon wavelength range of 300–2500 nm), respectively. Electrical conductivity (σ), charge-carrier concentration (n), and Hall mobility (μ_H) were measured at temperatures ranging from 143 to 400 K. It was found that more indium-rich films have higher energy gaps than less indium-rich ones while more Cu-rich films have lower energy gaps than less Cu-rich films. The sub-bandgap absorption of photons is minimum in the samples having Cu/In ≈ 1 and it again decreases, as Cu/In ratio becomes less than 0.60. Indium-rich films show n-type conductivities while near-stoichiometric and copper-rich films have p-type conductivities. At 300 K σ, n and μ_H of the films vary from 2.15 × 10⁻³ to 1.60 × 10⁻¹ (Ω cm)⁻¹, 2.28 × 10¹⁵ to 5.74 × 10¹⁷ cm⁻³ and 1.74 to 5.88 cm² (V s)⁻¹, respectively, and are dependent on the composition of the films. All the films were found to be non-degenerate. The ionization energies for acceptors and donors vary between 12 and 24, and 3 and 8 meV, respectively, and they are correlated well with the Cu/In ratios. The crystallites of the films were found to be partially depleted in charge carriers.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

Optical and structural characterizations of Cu-doped KCl films

The production of highly Cu⁺-doped KCl films and the properties of their 266 nm absorption band, which has an off-center property in doped single crystals, open the possibility of application of these films as ultra-violet optical filters. The investigated films, of approximately 1 μm thickness, were prepared by resistive co-evaporation of KCl and CuCl powders on different substrates of CaF₂, Al₂O₃, SiO₂, KCl and Si. The Cu⁺ concentration, as determined by energy-dispersive X-ray, ranges from 10²⁰ to 10²¹ cm⁻³, for 1–15% CuCl nominal mole percent concentration. Structural and optical properties were investigated through scanning electron microscopy, X-ray diffraction, ellipsometry, optical absorption and transmission. The films are polycrystalline, and the gain size decreases with increasing Cu⁺ impurity concentration, yielding an increase of visible transmission to a limited CuCl concentration. These films show a 6.295 Å lattice parameter with a f.c.c. structure and an index of refraction of 1.53 at 266 nm. When the Cu⁺ concentration is increased, the UV band position remains the same and no clusters are evidenced even to the high 15% CuCl concentration investigated, which differs very much from single crystals samples grown by the Kyropoulos-Czochralski method. For a Cu⁺ concentration of 8×10²⁰ cm⁻³ the film shows a transmission better than 88% at 350 nm wavelength.     

Hartree–Fock study of near-edge gap states in CaF2 with Na, Cl or Sr impurities

The energy of formation and electronic structure of Na⁺, Cl⁻ and Sr²⁺ impurity centers in CaF₂ have been computed using ab initio Hartree–Fock theory and the supercell approach. The work extends and complements recent results [Solid State Commun. 118 (2001) 569] for Mg²⁺ as a substitutional impurity in CaF₂. For Na⁺ substituting for Ca²⁺ [S(Na)], charge compensation by an F⁻ vacancy [V(F)] or by a second, interstitial Na⁺ [I(Na)] are both considered. In all cases, geometry optimization is done by relaxing the positions of nearest- and next-nearest-neighbors to minimize the total energy. After correction for electron correlation, the energies of formation increase in the order Mg²⁺2+−+ results are in agreement with previous Mott–Littleton formation energies. Ion charges, charge density maps and Mulliken bond populations are obtained to show the nature of bonding in the vicinity of the defect. Na⁺ leads to states just above the CaF₂ valence band maximum (VBM), and Na⁺ (and also Mg²⁺) produce states just below the conduction band minimum. The results are in qualitative agreement with available optical data for Na⁺ and Mg²⁺ impurity effects on CaF₂ near-edge absorption but show that gap states are important in addition to perturbed excitons. A Cl⁻ impurity yields a narrow band of states above the VBM which may significantly affect the deep-ultraviolet transmission of CaF₂. Sr²⁺ does not appear to produce states in the CaF₂ gap.     

A large area liquid scintillation multiphoton detector

A 60 layer lead-liquid scintillator shower detector, which we call the SLIC, has been used for multiphoton detection in the Fermilab tagged photon spectrometer. The detector has an unimpeded active area which is 2.44 m by 4.88 m and is segmented, by means of teflon coated channels, into 3.17 cm wide strips. The 60 layers in depth are broken into three directions of alternating readouts so that three position coordinates are determined for each shower. At present the readouts are made by 334 photomultiplier tubes coupled to BBQ doped wavelength shifter bars which integrate the entire depth of the detector. It is relatively straightforward to increase the number of readouts to include longitudinal segmentation and to increase the segmentation of the outer region which are at present read out two strips to a readout. The energy and position resolutions of isolated showers are about and 3 mm., respectively. The SLIC has been used to study the K⁻π⁺π⁰ decay of the D⁰ [1], as well as for electron and muon identification in ψ → e⁺e⁻ and ψ → μ⁺μ⁻ plus π⁰ identification in γp → ψχ [8].