Laser ablated bismuth cuprate thin films preparation and effect of oxygen nonstoichiometry upon superconductivity

Thin films of Bi₂Sr₂CaCu₂O₈ and (Bi, Pb)₂Sr₂Ca₂Cu₃O₁₀ have been prepared on monocrystalline (100) MgO substrates, using a laser ablation method with post annealing treatment. The influence of substrate temperature and oxygen pressure during deposition were investigated. SEM observations, EDS analysis, electric and magnetic measurements have been used to characterize the films. Superconducting “2212” films, with T_c(R = 0) at 80–83 K and J_c (50 K) up to 5 × 10⁵ A/cm², have been currently achieved, while Pb-doped “2223” films exhibit T_c as high as 110 K with J_c = 5 × 10⁴ A/cm² at 77 K. The effect of annealing at low temperature (350°C) in an argon flow has been studied for the 2212 phase, it shows the influence of the oxygen non-stoichiometry, i.e. of the hole carrier density upon T_c's which can be measured up to 89 K (zero resistance).     

Surface tension and density measurements for indium and uranium using a sessile-drop apparatus with glow discharge cleaning

The sessile-drop method is used to measure the surface tension and density of liquid indium and uranium under high vacuum. Measurements are made over the temperature range 156–500°C for In and at the melting point for U. Surface oxides are efficiently removed with a glow discharge system. Drop profiles are captured by photograph and processed using nonlinear regression to yield the surface tension and density. In this regression procedure, normal distances from calculated profiles to data points are minimized. For indium, the density and surface tension measurements yield _mp = 7.05 × 10³kg/m³, d/dT = −0.776 kg/m³·°C, and γ_mp = 0.568 N/m, dγ/dT = −9.45 × 10⁻⁵ N/m·°C. The results for uranium at the melting point are _mp = 17.47 × 10³ kg/m³ and γ_mp = 1.653 N/m.     

Oxygen tracer diffusion in La1 − xSrxCoO3

Tracer diffusion of ¹⁸O in dense, polycrystalline La_1−xSr_xCoO₃ for x = 0.1 has been measured in the temperature range 400 to 600 °C and at 500 °C for x = 0.2 at an oxygen partial pressure of 1 × 10⁵ Pa. Depth profiles were obtained by secondary ion mass spectrometry. The diffusion coefficient for La_0.9Sr_0.1CoO₃ is given by D = (17–247) exp[(−232 ± 8 kJ/mole)/RT] cm²/s. This value is several orders of magnitude lower than D extrapolated from the results for x = 0.2 measured in the 700–900 °C temperature range. One possible explanation for the discrepancy is that the two measurements reflect different diffusion paths. As expected, La_0.8Sr_0.2CoO₃ exhibits a higher diffusivity at 500 °C than does La_0.9Sr_0.1CoO₃.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

The effects of substrate temperature on the superconducting properties of Tl2Ca2Ba2Cu3O10 films sputter-deposited from stoichiometric oxide targets

The annealing characteristics and the superconducting properties of Tl₂Ca₂Ba₂Cu₃O₁₀ thin films sputter-deposited onto yttrium- stabilized ZrO₂ substrate at up to 500°C from two stoichiometric oxide targets are reported. The films deposited at 400–500°C were found to require a lower post-annealing temperature than the films deposited at lower temperatures to attain the highest T_c superconducting state, due to a more pronounced Ba diffusion toward the substrate as indicated by their secondary ion mass spectrometry depth profiles. The highest T_c achieved tends to degrade with increasing substrate temperatures, a zero resistance T_c of 121 and ≈90 K, respectively, being observed for the films deposited at -ambient temperature and at 500°C. The formation of the highest T_c phase (Tl₂Ca₂Ba₂Cu₃O₁₀) generally is associated with a sheet type of crystal growth morphology with smooth and aligned surfaces which can be obtained only from the films capable of sustaining prolonged annealing at 900°C. Annealing at lower temperatures (≈860°C) results in the formation of rod or sphere type of morphologies with rough and randomly oriented crystals and the lower T_c phases such as Tl₂Ca₁Ba₂Cu₂O₈.     

The effect of a nitrogen-rich surface layer on the sub-surface deuterium (hydrogen) concentration distribution in titanium

Deuterium and nitrogen depth profiles in Ti with modified surfaces have been measured with Auger electron spectroscopy, secondary ion mass spectroscopy, and D(³He,p)⁴He nuclear reaction analysis. Nitrogen-rich surfaces layers of varying thicknesses were created on Ti by exposure to N₂ gas at 650°C. Deuterium loading was performed by exposure to 1 Torr of D₂ gas at 500°C. The deuterium distribution was influenced by nitrogen in the near-surface regions of all samples. Specifically, deuterium solubility was suppressed in surface regions of high (greater than 1%) nitrogen concentration. The deuterium solubility also remained low within the first few microns, well beyond the region of high nitrogen concentration. This effect is attributed to internal elastic stresses imposed by the non-deuterium absorbing nitrogen-rich layer on the Ti. These stresses prohibit the volume expansion associated with deuterium absorption. We estimate stresses on the order of 3–4 GPa are required to suppress the deuterium solubility to the values observed. The deuterium absorption kinetics were observed to depend systematically on the thickness of the nitrogen-rich layer. This is consistent with limited solubility near the surface or a surface poisoning effect influencing the overall deuterium diffusion from the gas phase into the Ti bulk.     

Transport properties of SrCe0.95Y0.05O3−δ and its application for hydrogen separation

Transport properties of SrCe_0.95Y_0.05O_3−δ were studied by impedance spectroscopy and by measuring open-cell voltage (OCV) and gas permeation. Ionic transference numbers were determined by measuring the OCV of concentration cells and water vapor evolution of an O₂/H₂ fuel cell. We observed interfacial polarization on the basis of the I–V curves obtained by discharging a hydrogen concentration cell or an O₂/H₂ fuel cell. The observed high protonic conductivity (high proton and low oxide ion transference numbers) makes SrCe_0.95Y_0.05O_3−δ a potential material for hydrogen separation. From proton conductivity measurements, under a given hydrogen partial pressure difference of 4%/0.488%, the hydrogen permeation rate (of a dense membrane with 0.11 cm in thickness) was calculated to be ≈0.072 cm³ (STP) cm⁻² min⁻¹ at 800°C, whereas the permeation rate calculated from short-circuit current measurements was ≈0.023 cm³ (STP) cm⁻² min⁻¹ at 800°C. The difference between calculated and observed permeation rates is probably due to interfacial polarization.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

The energy levels of Al

The energies and strengths of ²⁵Mg(p, γ), ²⁵Mg(p, p₁) and ²⁵Mg(p, p₂) resonances were determined in the energy range E_p < 2 MeV. Four new (p, γ) resonances were observed at E_p = 736.2±0.7, 818.1±0.7, 834.6±0.7 and 1514.7±0.7 keV. The γ-decay of 44 resonances and 49 bound levels was established. The energies of 41 and mean lifetimes of 25 bound levels were determined. Two new levels at E_x = 4952.4±1.4 keV and 5141.7±2.0 keV were observed. Angular distributions yielded unique spins for five resonance levels. Weisskopf estimates allowed unique spin assignments for five resonances. The Q-value of the ²⁵Mg (p, γ) ²⁶Al reaction was found to be 6305.0±1.2 keV.     

Effect of different oxidizing gases on the in-situ growth of YBa2Cu3O7−δ films by pulsed laser deposition

The effectiveness of oxygen (O₂), nitrous oxide (N₂O), and nitrogen dioxide (NO₂) as oxidizing agents during in-situ growth of YBa₂Cu₃O_7−δ (YBCO) films on (100) SrTiO₃ substrates by pulsed laser deposition has been studied as a function of deposition temperature (700–800°C), and laser wavelength (193,248 and 355 nm), for a wide range of oxidizer gas pressure (0.1–200 mTorr). In general, the superconducting transition temperature of the films has been found to increase with increasing oxidant pressure, with zero-resistance temperature ≈90 K only obtained in films prepared in a relatively high pressure (150–200 mTorr) of oxidizer gas. At lower pressures, the transition temperature while being depressed is quite sensitive to the nature of the oxidant, the laser wavelength and the deposition temperature. Nevertheless, independent of the oxygen source or other growth parameters, an almost linear decrease in transition temperature with a corresponding increase in the c-axis lattice parameter has been observed for all the film. YBCO films have also been deposited in a low pressure background (≤ 1 mTorr) using a combination of atomic oxygen and pulsed molecular oxygen. The results are discussed in terms of the oxygen requirement for kinetic and thermodynamic stability of YBCO during growth of the film by pulsed laser deposition.     

Buffers for high temperature superconductor coatings. Low temperature growth of CeO2 films by metal–organic chemical vapor deposition and their implementation as buffers

Smooth, epitaxial cerium dioxide thin films have been grown in-situ in the 450–650°C temperature range on (001) yttria-stabilized zirconia (YSZ) substrates by metal–organic chemical vapor deposition (MOCVD) using a new fluorine-free liquid Ce precursor. As assessed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution electron microscopy (HREM), the epitaxial films exhibit a columnar microstructure with atomically abrupt film-substrate interfaces and with only minor bending of the crystal plane parallel to the substrate surface near the interface and at the column boundaries. With fixed precursor temperature and gas flow rate, the CeO₂ growth rate decreases from 10 Å/min at 450°C to 6.5 Å/min at 540°C. The root-mean-square roughness of the films also decreases from 15.5 Å at 450°C to 4.3 Å at 540°C. High-quality, epitaxial YBa₂C₃O_7−x films have been successfully deposited on these MOCVD-derived CeO₂ films grown at temperatures as low as 540°C. They exhibit T_c=86.5 K and J_c=1.08×10⁶ A/cm² at 77.4 K.     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.     

Synthesis and physical behaviour of In2S3 films

In₂S₃ layers have been grown by close-spaced evaporation of pre-synthesized In₂S₃ powder from its constituent elements. The layers were deposited on glass substrates at temperatures in the range, 200–350 °C. The effect of substrate temperature on composition, structure, morphology, electrical and optical properties of the as-grown indium sulfide films has been studied. The synthesized powder exhibited cubic structure with a grain size of 63.92 nm and S/In ratio of 1.01. The films grown at 200 °C were amorphous in nature while its crystallinity increased with the increase of substrate temperature to 300 °C. The films exhibited pure tetragonal β-In₂S₃ phase at the substrate temperature of 350 °C. The surface morphological analysis revealed that the films grown at 300 °C had an average roughness of 1.43 nm. These films showed a S/In ratio of 0.98 and a lower electrical resistivity of 1.28 × 10³ Ω cm. The optical band gap was found to be direct and the layers grown at 300 °C showed a higher optical transmittance of 78% and an energy band gap of 2.49 eV.     

Characterization of high-k gate dielectric/silicon interfaces

We have shown that, for thermally evaporated Ta₂O₅ or ZrO₂ thin films on Si(1 0 0), O₂ annealing at 300–500 °C causes the formation of an interfacial silicon oxide layer as thin as 1–2 nm which can be interpreted in terms of their high permeability to oxygen. And we have demonstrated how useful the energy loss spectra of photoexcited electrons from core levels such as O 1s are to measure the energy bandgaps of very thin insulators. With the combination of measured bandgaps and valence band lineups determined for X-ray photoelectron spectroscopy valence band spectra, we have determined the energy band alignments of Ta₂O₅ and ZrO₂ with Si(1 0 0) before and after the O₂ annealing at 500 °C. In addition, we have demonstrated that total photoelectron yield spectroscopy provides us direct information to quantify the energy distributions of both the defect states in the high-k dielectrics and the dielectric/Si(1 0 0) interface states over nearly entire Si bandgap.     

Measurements of interaction cross sections and radii of He isotopes

Secondary beams of ³He, ⁴He, ⁶He, and ⁸He were produced through the projectile fragmentation of an 800 MeV/nucleon ¹¹B primary beam. Interaction cross sections (σ_I) of all He isotopes of 790 MeV/nucleon on Be, C, and Al targets were measured by a transmission-type experiment. The interaction nuclear radii of He isotopes R_I(He) = (σ_I/π)^1/2 − R _I(T) where R_I(T) is the radius of the target nucleus, have been deduced to be R_I(³He) = 1.59 ± 0.06 fm, R_I(⁴He) = 1.40 ± 0.05 fm, R_I(⁶He) = 2.21 ± 0.06 fm, and R_I(⁸He) = 2.52 ± 0.06 fm.     

Superconducting oxide formation in the Yb---Ba---Cu---O system

Conditions for forming YbBa₂Cu₄O₈, Yb₂Ba₂Cu₃O_7−δ and YbBa₂Cu₃O_7−δ were determined in oxygen at 1.0 atm pressure by experiments with oxidized Yb---Ba---Cu---Ag alloys. YbBa₂Cu₃O_7−δ formed in less than 10 s when oxidized alloy ribbons were baked in the 805°C–890°C range. Large amounts of Ba₂Cu₃O₅ formed below 870°C. Yb₂Ba₄Cu₇O_15−δ and YbBa₂Cu₄O ₈ then formed in the 10²s–10³s range at temperatures in the 840°C–870°C and <840°C ranges, respectively. Ba₂Cu₃O₅ decomposition supplied Cu²⁺ and O²⁻ for the rapid transformation of YbBa₂Cu₃O_7−δ grains into Yb₂Ba₄Cu₇O_15−δ grains by intercalation. Intercalation was much slower in the absence of Ba₂Cu₃O₅. All of these transformation products underwent coarsening with increasing bake time. Rapid YbBa₂Cu₄O₈ and Yb₂Ba₄Cu₇O_15−δ formation, compared to the slow formation of these phase types when Yb was substituted by Y, Is due to the differing effects of Y and Yb on formation kinetics. Superconducting oxide-silver composite ribbons containing mainly YbBa₂Cu₃O_7−δ, Yb₂Ba₄Cu₇O_15−δ or YbBa₂Cu₄O₈ can be prepared from Yb---Ba ---Ba---Cu---Ag alloys.     

An electron back-scattering Mössbauer spectroscopy study of thin magnetite films

Magnetite films of thickness 16–282 Å were prepared by oxidation of thin ⁵⁷Fe films at 220°C in 5 × 10^-3 Torr oxygen and investigated using electron back-scattering Mössbauer spectroscopy. At room temperature the internal hyperfine fields (H_int) due to the A and B site cations in Fe₃O₄ show a systematic decrease with decreasing film thickness. The spectrum from the 16 Å-thick oxide shows collapse of the magnetic patterns to give a superparamagnetic quadrupole split doublet. All spectra recorded at 12.5 K exhibit six broad peaks of a magnetically split pattern with H_int greater than at room temperature but showing little change with oxide thickness.     

High and low thermal nitridation of SiO2 thin films

Thin thermal SiO₂ films on crystalline silicon substrate were nitrided at low ammonia pressures (10^-6P_NH310^-1 mbar) for times varying from 1 to 10 h, by means of two techniques. (i) Surface nitridation has been achieved by thermal activation at high temperature (HT), in the range 800–1100°C. (ii) A new process at low temperature (LT), was employed at T ≈ 30°C, under electron-beam irradiation; the nitridation-reaction rate depends on the electron energy (reaching a maximum within the energy range 1 to 2 keV), and on the electron flux. Conduction and electron trapping on the nitrided oxide films depends on the chemical compositions and on the amount of nitrogen incorporated into the bulk of the films and/or at the SiO₂-Si interface.     

The Bi(d,γ)Po reaction

The yield of the ²⁰⁹Bi(d, γ)^211g.s.Po and ^211mPo (T_1/2 = 25.2s) reaction was measured for deuteron energies E_d = 8–11.5 MeV. The reaction was identified by the -activities of the Po isotope. At E_d = 10.43 MeV, the (d, γ) cross section for the population of the ground state of ²¹¹Po is σ_g.s. = 16 ± 3 μb, the ratio relative to the cross section for the metastable state is σ_g.s./σ_m = 25.4 ± 0.9. These values and the yield curves were compared with calculations using a simple model for the population of the two states. In the excitation region E* = 15–19 MeV, the branching ratio of γ- to particle emission is nearly constant and has a value of about 0.4 × 10⁻⁴.     

Duree de vie et depolarisation par collisions avec l''helium des niveaux 5P3/2 Et 5P1/2 de l''ion Cd

The lifetimes of the Cd⁺ 5²P_3/2 and 5²P_1/2 states have been measured by the Hanle effect. The Cd⁺ ions are produced in a d.c. discharge in cadmium vapor, with helium as buffer gas. The results are: τ(5²P_3/2) = (2.60±0.20) ×10⁻⁹sec, and τ(5²P_1/2) = (3.05 ± 0.13) × 10⁻⁹sec.

We measured also the cross sections for the destruction of the orientation in the 5²P_1/2Cd⁺ state (<5Ų), of the orientation (18±10Ų) and of the alignment (46±10Ų) in the 5²P_3/2 state due to collisions with the helium atoms.