Thermodynamic analysis and technology of preparation of high-Tc superconducting system YBa2Cu3O7−x

By modeling the equilibrium state of the phase formation reaction of High-T_c superconducting phase 1:2:3 (YBa₂Cu₃O_7−x) and using the results of P-T−x correlation investigation of some authors, the variation of Gibbs free energy (ΔGm) versus temperature has been calculated. On the basis of the variation of ΔGm, the technology procedure of preparation of phase 1:2:3 with desired x has been established to meet requirement of basic investigation and application of High-T_c superconductors YBa₂Cu₃O_7−x.     

Magnetic and electric properties of the ternary alloys AB

The results of experimental studies of the electrophysical and magnetic properties of solid solutions based on the AB compounds with anion (Zn₃(P_xAs_1−x)₂ and cation (Zn_xCd_1−x)₃ P₂ substitution are reported. The Zn₃(As_xP_1−x)₂ solid solutions are characterized by p-type conductivity (∼ 10¹⁵  10¹⁷ cm⁻³), low Hall mobility and conductivity of ∼ 10⁻² — 10⁻³ ohm⁻¹ cm⁻¹. In the (Zn_xCd_1−x)₃P₂ solid solutions the samples rich in zinc are p-type, those rich in cadmium — n-type, the carrier concentration is ∼ 10¹⁶ — 10¹⁸ cm⁻³. From the measurements of the magnetic properties of the above mentioned alloys it is shown that in the investigated solid solutions a transition from the structure with direct optical transition to those with indirect optical transition occurs.     

Temperature profile and homogeneity of the growth rate of CVD Silicon from SiH4-HCl-H2 mixtures

With the aid of the methods of the statistical design of experiments for each wafer site (x) on the graphite susceptor an empiric polynomial was obtained for CVD epitaxial silicon from SiH₄–HCl–H₂ mixtures, linking the growth rate v_epi to the process parameters p⁰, p⁰_HCl, and T(x). By means of the statistical model optimum temperatur characteristics along the susceptor were selected and discussed for specific deposition conditions.     

Growth of bulk zinc chalcogenide single crystals from the vapour phase and their use for laser screens of projection colour television

Results on ZnSe, ZnSe_xS_1−x and ZnS crystal growing from the vapour phase up to 7.5 cm³ in volume are described. Crystals were grown on sapphire, ZnS, ZnSe_xS_1−x and quartz glass substrates without a contact of the growing crystal with a growth ampoule and using the molten tin as a heating medium. Large high-purity crystals with a density of etch pits of 10³ cm⁻² were obtained They exhibited an effective exciton luminescence and rather high radiation efficiency (30 ± 10% for ZnSe at T = 77 K). This made it possible to use these crystals for fabricating laser screens for a cathode ray tube. The main laser parameters obtained on a ZnSe screen at T = 80 and 300 K using a 75 keV electron beam excitation are presented. The light power output reached 0.8 W at T = 80 K; this allowed to obtain a 10 cd · m⁻² TV image of 1.5 × 2 m² in area.     

The influence of small deviations from stoichiometry on the properties of Y?Ba?Cu?O superconductor ceramics

According to a central composite design samples with deviations from stoichiometry YBa₂Cu₃O_7−x of ±2.5 wt% in the ingredients were prepared. The influence of these deviations on phase content, superconducting properties and microstructure of the ceramics was studied.     

The precipitation of sparingly-soluble metal salts from aqueous solution: Heterogeneous nucleus numbers at low to intermediate supersaturation

The precipitation of series of alkaline-earth metal and transition hydroxides, sulphates, chromates and molybdates, hydrogen phosphate carbonates, oxalates and ‘oxinates’ were studied in aqueous solution of low to intermediate supersaturation. Heterogeneous nucleation probably occurred onto micro-crystalline particles of some siliceous mineral (of the trigonal, hexagonal or cubic system), dispersed in the solution. The heterogeneous nucleus numbers for these precipitations then depended on the rates of the heterogeneous nucleation onto these substrates and the rates of the mononuclear growth of nuclei to crystallites (during the induction periods). Generally, N_het values in polypropylene and glass beakers, at low supersaturation, varied from 10⁴ to 10¹³ dm⁻³: the N_het values then increased slightly with concentration and supersaturation according to the relation N_het = K_N^β, where K_N is a function of the metal salt surface energy and an ‘epitaxy’ factor; β = 0.4–0.5. In turn, at any supersaturation, log N_het = log N + Fσ, where N and F were constants for any precipitation: N_het values then increased from 10⁴ to 10⁸ times for increase in σ from 50 to 150 mJ m⁻². At any supersaturation and surface energy, N_het values increased in the order monoclinic < orthohombic < tetragonal < trigonal crystals.     

Hyperfine structure of EPR spectra of Cr5+ ions in irradiated sodium dichromate crystals

EPR spectra are studied of X-irradiated sodium dichromate crystals grown from an aqueous solution by evaporation at 31°C. Doublet lines of EPR-absorption are attributed to the Cr⁵⁺ ions in the CrO₄³⁻ and CrO₃⁻ radicals resulting from radiation decomposition of Cr₂O₇²⁻ and being in the lattice in two unequivalent positions. Hyperfine structure caused by interaction of an unpaired electron with Cr⁵³ nucleus were observed both at liquid nitrogen and room temperatures. For the line, caused by CrO₄³⁻ radical, g_y and A_y directions coincide and angles both between A_x, g_x and A_z, g_z make up ∼ 25°. The spectrum is described by usual spin Hamiltonian for S = 1/2 with following parameters (T = 77 K): for CrO: g_z = 1.984, g_y = 1.970, g_x = 1.961, |A_z| = 8.2 · 10⁻⁴ cm⁻¹, |A_y| = 13.7 × 10⁻⁴ cm⁻¹, |A_x| = 36.1 · 10⁻⁴ cm⁻¹; for CrO₃⁻: g_z = 1.915, g_y = 1.975, g_x = 1.985, |A_z| = 32.2 · 10⁻⁴ cm⁻¹.     

Interactions between YBa2Cu3O7-x and K2Co3

The interactions between YBa₂Cu₃O_7-x and K₂CO₃ have been studied using thermochemical methods, isothermal annealing of diffusion pairs, optical microscopy, X-ray diffraction, and microprobe analyses. The experiments have shown existence of solubility of YBa₂Cu₃O_7-x or its constituents in both solid and liquid K₂CO₃. The barium ions are preferably dissolved in K₂CO₃, whereas potassium cations do not enter massively into the bulk of the YBa₂Cu₃O_7-x-phase. A eutectic-type phase diagram is supposed for the system K₂CO₃–YBa₂Cu₃O_7-x. The so called “green phase” Y₂BaCuO₅ and a K–Cu–O compound have been found in the contact zone at 813 °C while a “black phase” layer with nominal composition Y_1.6Cu_2.8O_5.4 has grown at 707 °C.     

Magneto‐transport properties of polycrystalline YBa2(Cu1‐xMx)3O7‐δ (M = B and Mn)

The magnetic and transport properties of polycrystalline YBa₂ (Cu_1‐xM_x)₃ O_7‐δ (M = B and Mn) superconductor was investigated. Samples of YBa₂(Cu_1‐xB_x)₃O_7‐δ doped with several concentrations of boron B(x = 0.05 and 0.1) were investigated using magnetization measurements. A YBa₂(Cu_1‐xMn_x)₃O_7‐δ sample doped with Mn with concentration of x = 0.02 was investigated using current‐voltage (I‐V) measurements. Our results on the YBa₂(Cu_1‐xB_x)₃O_7‐δ samples reveal a considerable increase in the hysterisis width of the magnetization, M versus the applied magnetic field H with increasing boron concentration. The lower critical field was also found to be enhanced by boron doping. The critical current density, J_c was found to be significantly enhanced in the Mn‐doped sample. The enhancement of J_c was found to be more significant at the lower temperatures for all applied magnetic fields used (0 Oe, 300 Oe, and 500 Oe). Thus, chemical doping is suggested to enhance the vortex pinning forces in the YBCO samples. From the resistivity (R‐T) measurements, chemical doping of the samples was found to have no significant effect on the critical temperature, T_c. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Incorporation concentration dependence of phosphorus in the deposition of silicon epitaxial layers from silane-phosphine-hydrogen mixtures

The empirical incorporation characteristic N with the phosphine input pressure (P) as the controlling variable and the phosphorus incorporation concentration ((14 < lg N<18)) as the controlled variable is theoretically explained by comparing the thermodynamic equilibrium pressures of the various phosphorous hydrides and the various molecular species of the phosphorus vapour in the Si P H system in their respective incorporation equilibria with regard to the phosphorus incorporation concentration. In the lower incorporation concentration range (lgN > 18) there is an almost total agreement of the values of the phosphine equilibrium pressure (PPH_j; j = 2; 3) and the phosphine input pressure. In the upper concentration range (lg N > 18) there is a close approximation of the equilibrium partial pressure of the dimeric phosphorous vapour (PP₂) to the phosphine input pressure. There is no marked effect of the conduction electron density in silicon at the deposition temperatures considered on the incorporation characteristic.     

Strukturelle Umklapp-Vorgänge in metastabilen β1-Kupfer-Zink-Mischkristallen bei tiefen und höheren Temperaturen (I). Gitterdynamische Skizze1)

The quantity of the shear-modulus G′ = (c₁₁ – c₁₂)/2 is a measure for the probability of structural Umklapp-processes to occur in metastable β₁-Cu-Zn-solid solutions. Such processes take place, if G′ = G′(T, x) would fall below a critical limit, G′_crit, e.g. by lowering of temperature T or/and Zn-concentration x, because the Fermi-contribution to G′will sink in the 1^st and with him additional the Coulomb-contribution in te 2^nd case. Both ones are the authoritative stabilizing factors for β₁ and therefore specific fo its lattice-dynamical behaviour, especially in the longwavy range of thermoacoustic lattice-vibrations, by which the cooperative Umklapp-motion will escape. Umklapping can also be initiated by favourably oriented dislocations, is G′ would approach to G′_crit in their neighbourhood: G′_critG′(xM8), with xM8  Umklapp-concentration. This is possible by variation of x during isothermal reactions, in the course of whicht he β₁-matrix will heterogenize itself into Zn-poorer and -richer districts β and β (pre-diffusion by means of quenchy vacancies). Both kinds of districts, among which the latter ones will enhance their degree of stability, are joint together coherently. They build up a so called β /β -parquet. The parquet-bricks can reach a critical size, which is necessary that sufficient large atom-collectives can simultaneously be caused to an Umklapp-motion and to occupate new equilibrium positions by thermo-acoustic shear-waves (comparison with a sin-wave beeing changed to a zigzag-line). Only at higher temperatures the bricks come up to the critical size. Umklapping comes about only in the β -bricks, which turn by it to a transition lattice (β₂) with a structure similary to that of the lowtemperature-martensite β′′. After that β₂ changes to α-phase. The way β ⇒ α is marked by the following steps: prediffusion, Umklapping + dislocation, leading to β₂, and a further dislocation dissoziation, leading the atoms to the equilibrium positions in the α-lattice. The so stepped mechanism acts an nucleationmechanism of the α-phase. After the nucleation the α-nuclei grow at the cost of too much formed β (postdiffusion). By isothermal reactions at too low temperatures a mini-herterogenized state of the β₁-matrix will be caused comparable with coldhardening states of other alloys (Guinier-Preston-zones). A β₁-matrix in such a state is unable to isothermal Umklapping, so that α-crystals can be formed – provided that the mini-heterogenities are resolved by increasing of the reaction temperature.     

Impurity band conduction effects in liquid phase epitaxial Te-doped GaP grown from tin solution

GaP layers were grown by liquid phase epitaxy from tin solution on semi-insulating GaAs substrates with various amounts of Te added to the melt (x_Te = 10⁻⁴ …︁ 3 · 10⁻²). The Sn and Te concentrations in the layers were determined by chemical analysis as function of x. An analysis of the electrical measurements shows that the carrier transport in the layers is essentially determined by impurity band conduction effects.     

The precipitation of sparingly-soluble metal ‘oxinates’ induction periods and nucleation rates

The precipitation of barium, strontium, calcium, magnesium, zinc, cadmium, lead, cobalt, nickel and copper 8-quinolinolates (‘oxinates’) was studied in buffer solutions (pHs from 10 to 4.5) at 22 °C: the metal cation and overall ‘oxinate’ with ‘oxine’ concentrations were varied from 0.0005 to 0.010 M (and saturation rations varied from 3 to 3.000). The induction periods, before the main growth surge, were measured at different metal oxinate concentrations (C) and saturation ratios S = (C)/S · P_r^1/3. Nucleation rates were determined from combined measurements of induction periods and final crystal numbers. Nucleation rates varied with saturation ratios according to the relation \documentclass{article}\pagestyle{empty}\begin{document}$ R_n = k_1 \cdot S^8 {\rm\ nuclei cm}^{ - {\rm 3}} {\rm sec}^{ - {\rm 1}} $\end{document} Induction periods decreased with increasing concentration and supersaturation; over the range t > 3.000 to < 1 sec, . Where t and t were factors that depended on nucleation rates and metal salt solubility. t values decreased and t values increased with decreasing solubility. Precipitation occurred through homogeneous nucleation. Low nucleation rates and prolonged induction periods in solutions of medium to high supersaturation were related to slow rate-determining stages in nucleus formation and to complex formation between metal cation and oxinate anion.     

Dependence of doping element incorporation on temperature in the chemical vapour deposition of epitaxial silicon (III). Empirical incorporation characteristic of the Si-P-H system

The shape of the empirical incorporation characteristic of phosphorus in epitaxial silicon, deposited from silane-phosphine-hydrogen mixtures, shows two branches with different incorporation dependences on temperature (incorporation enthalpies). In the lower phosphorus-concentration range (N < 10¹⁸) the experimentally determined value of incorporation enthalpy can be explained as a complex quantity, including the enthalpies of the two phosphorus hydrides PH₃ and PH₂, the latter of which is formed by the partial decomposition of phosphine (PH₃) at deposition temperatures. — In the upper phosphorus-concentration range (N > 10¹⁸) the incorporation equilibrium of the dimeric phosphorus molecules, formed by the nearly complete decomposition of phosphine, is reflected in the incorporation enthalpy of the empirical incorporation characteristic.     

Temperature variation of the structural and thermal characteristics of YBa2Cu3O7−x in the range from 90 to 400 K

The X-ray studies of the tetragonal YBa₂Cu₃O_7−x compound are performed at different temperatures from 400 to 90 K and the temperature variation of the thermal expansion coefficients and the Debye characteristic temperature is determined. The anisotropy of thermal expansion is investigated. It is found that the two dynamical characteristics monotonously decrease with temperature lowering whereas for the superconducting orthorhombic modification their temperature dependences are anomalous. The mean thermal expansion coefficient as well as the overall Debye temperature for the tetragonal phase are smaller than those for the orthorhombic one.     

Heterophase states and a bridging phase in (1‐x)BiScO3 − xPbTiO3

Heterophase ferroelectric solid solutions of (1‐x)BiScO₃ − xPbTiO₃ are studied near the morphotrpic phase boundary (0.60 ≤ x ≤ 0.64). The role of non‐180° domain types of the P4mm and R3m phases in heterophase structures is studied in the context of the phase content. It is shown that the bridging Cm phase coexists with the adjacent phase (either P4mm or R3m), and different variants of an elastic matching ‘single‐domain Cm phase–polydomain P4mm phase’, ‘single‐domain Cm phase–polydomain R3m phase’ and ‘single‐domain Cm phase–near single‐domain R3m phase’ promote the complete stress relief. Based on these concepts and considering a minimum number of the domain types in the coexisting phases, we find a molar‐concentration dependence of the volume fraction of the Cm phase in the heterophase states. A correlation between the predicted volume fraction of the Cm phase and ratios of its unit‐cell parameters is first revealed. The role of the intermediate R3m phase in the phase sequence R3c − R3m − Pm$\overline 3$m and in the stress relief at x = 0.60 is discussed. Good agreement between the predicted and experimental data on the phase content is reached near the morphotrpic phase boundary.     

Mathematical Description of Strongly Nonlinear Pressure Dependence of Phase Transition Temperatures

In order to describe mathematically the pressure dependence of phase transition temperatures we have derived an equation using the following assumption: i. The transition enthalpy Δ_tH = const. ii. The transition volume Δ_tV depends on the pressure p according to: The modified Simon-Glatzel-equation T = T₀(1 + p/b)^a exp (cp) allows to calculate the transition temperatures T also in cases of strongly non-linear relations.     

Infrared optical properties of Cu1−xLixSe2 thin films

Infrared absorption spectra of Cu_1−xLi_xInSe₂ thin films are measured at room temperature in the wavenumber range from 100 to 600 cm⁻¹. The spectra exhibit two absorption bands in the wavenumber ranges 200–210 cm⁻¹ and 330–355 cm⁻¹ which are ascribed to vibrational modes due to In Se and Li Se vibrations, respectively. The influence of the phase transition from the chalcopyrite structure to the β-NaFeO₂ structure in the composition range x = 0.5–0.6 on the vibrational characteristics is established and discussed.     

Antisolvent crystallization of aqueous ammonium dihydrogen phosphate solutions by addition of acetone at different rates

Results of an investigation of in situ measurements of laser‐beam intensity I_s and I_m transmitted through aqueous ammonium dihydrogen phosphate (ADP) solutions saturated at 30 °C and water, respectively, and temperature T_s of solution and T_m of water during feeding of antisolvent acetone at different rates R_A, using an indigenously designed experimental setup, are presented and discussed. It was found that: (1) for the measurement of MSZW, defined as the maximum volume fraction of acetone content Δx_max in the solution, obtained from temperature measurements are more reliable than transmitted laser‐beam intensity measurements for solutions, (2) two minima ΔT_min1 and ΔT_min2 associated with endothermic reactions, separated by a maximum ΔT_max due to exothermic reactions appear in the plots of temperature difference ΔT = T_s−T_m against acetone feeding time t, and (3) in the ΔT(t) plots there are time intervals Δt of constant rates R_T of increase in ΔT of aqueous ADP solutions, and these values of R_T increase linearly with acetone feeding time rate R_A. The experimental data on the observed dependence of MSZW on antisolvent feeding rate R_A, the appearance of minima ΔT_min1 and ΔT_min2 and maximum ΔT_max and their dependence on R_A, and the relationship between R_T and R_A are discussed from consideration of processes of nucleation and growth of crystallites.