TSC study of electric dipole relaxations in chlorapatite

Electric dipole relaxations in chlorapatite, Ca₅(PO₄)₃Cl, have been studied with the fractional polarization mode of the thermally stimulated currents (TSC) method. Fifty-one of the fifty-seven sets of data obtained in the range 10–443°K fell naturally into four groups yielding compensation temperatures T_C of T_C1, = 202°C, T_C2: = 202°C, T_C3 = 420°C and T_C4= 644°C, with estimated error < 10°C, and characteristic relaxation times τ_C of τ_C1 = 1.3 × 10^?7s, τ_C2 = 3.2 × 10^?6s, τ_C3 = 8.8 × 10^?5s and τ_C4 = 2.3 × 10^?4s. Atomic-scale physical models involving Cl^? ion motion are offered for the 202°C compensation at the temperature of the reported monoclinic-to-hexagonal phase transition and for the 420°C compensation, at which temperature the Cl^? ions individually are thought to have enough thermal energy to maintain the hexagonal form dynamically.     

Elastic constants of sodium chlorate from 77 K to 350 K

The elastic constantsC ₁₁,C ₁₂ andC ₄₄ of sodium chlorate single crystal have been evaluated using 10 MHz ultrasonic pulse echo superposition technique. The values areC ₁₁=4.90,C ₁₂=1.39,C ₄₄=1.17 (× 10¹⁰ N/m ²) at 298 K and 6.15, 2.16, 1.32 (×10¹⁰ N/m ²) at 77 K. The data agree well with the values measured earlier up to 223 K. Brief mention is also made of the low temperature bonding problems in these soft crystals.     

A note on the elastic constants of sodium bromate from 350 K to 77 K

The elastic constantsC ₁₁,C ₁₂ andC ₄₄ of sodium bromate single crystals have been evaluated using 10 MHz ultrasonic pulse echo superposition technique. The values areC ₁₁=5.57₈,C ₁₂=1.07₅,C ₄₄=1.51₀ (×10¹⁰ N/m²) at 290 K and 6.35, 1.98 and 1.65 (×10¹⁰ N/m²) at 77 K. The present room temperature values agree closely with the recent values of Gluyaset al. but the other earlier measurements show some scatter. A comparison between the elastic constants of sodium bromate and sodium chlorate is also made.     

Magnetic susceptibility and superconductivity of cubic vanadium nitrides

The superconducting transition temperature T_C and the magnetic susceptibility from 77 to 300°K have been measured on five cubic vanadium nitrides: VN, VN_0.91, VN_0.82, VN_0.84 and VN_0.75. The materials were carefully prepared to exclude oxygen and ferromagnetic impurities.The value of T_C, falls from 8.1°K for VN to 2.3°K for VN_0.75. The mass-susceptibility decreases from +3.94 × 10^?6e.m.u./g for VN to 1.88 × 10^?6e.m.u./g for VN_0.75 at 300°K. All samples showed a small positive slope for the susceptibility temperature curve.The results are discussed in terms of the rigid band model. The main features are a high density of states of d electrons, 2.4 states/atom eV for VN that drops off as the nitrogen content decreases, to 0.8 states/atom eV.Preliminary considerations indicate that many-body effects could reduce this density of states by as much as a factor of 2. Lack of experimental results on Knight shifts and low-temperature specific heats prevent a more quantitative estimate being made.     

Indirect electronic transitions in alkali halate crystals-I (sodium and potassium chlorate crystals)

The long wavelength tail of the fundamental absorption in NaClO₃ and KClO₃ crystals has been analysed based on the theory of band to band transitions of Bardeen et al.[8] developed in the case of semi-conducting crystals. Evidence of phonon involvement in the transitions giving an indirect band gap is observed. The energies of the phonons involved in the process are the same for both the crystals, and agree well with combinations of prinicple frequencies of ClO₃^? ion, their overtones and also lattice phonons. The indirect band gap in these crystals varies with temperature more or less linearly and the rate of variation is ?3·8 × 10^?4 eV/K and ?5·0 × 10^?4 eV/K for sodium chlorate and potassium chlorate respectively.     

Measurements of intensities and nitrogen-broadened linewidths in the CO fundamental at low temperatures

Intensities and nitrogen-broadened half-widths of lines R(0), R(8) and R(16) in the fundamental band of ¹²C¹⁶O have been measured at 83°K, 100°K, 150°K, 200°K and 298°K. The intensities of several other lines in the P- and R-branches of the band have also been measured at 298°K. The absolute intensity derived from the line intensity data using the Herman-Wallis formula is S^°_v = 273 ± 10 cm^-2atm^-1 at S.T.P. A separate measurement employing the Wilson-Wells-Penner-Weber method has yielded S^°_v = 277 ± 4 cm^-2 atm^-1 at S.T.P. Both of these values are within 6 per cent of most of the previously published direct measurements of this parameter. The values for the line intensities reported earlier by other authors are lower by nearly 16 per cent.     

Halleffekt und anisotropie der beweglichkeit der elektronen in ZnO

Hallconstant, conductivity and Hall mobility of ZnO crystals were measured as function of temperature (4 °K < T < 370 °K) and orientation. Value and anisotropy of mobility can be explained (50 °K < T < 370 °K) by polar optical scattering, deformation potential sc., piezoelectric sc. and sc. by ionized impurities. The anisotropy of mobility is caused only by piezoelectric sc. Maximum values of μ_H are reached for μ_H ⊥ c, with 2400 cm²/V sec at 40 °K and for μ_H ¦ c with 1350cm²/Vsec at 60 °. Below 50 °K Hallconstant, conductivity and Hall mobility are influenced by impurity band conduction processes. The crystals have impurity concentration in the 10¹⁶ cm^?3 range, but they show different donor activation energies depending on growth conditions: Type I: 38,4 meV (50 °K < T < 100 °K) and Type II: 20,3 meV (50 °K < T < 100 °K) and 6 meV (25 °K < T < 50 °K).     

Classical dispersion analysis of the internal modes of sodium chlorate

The application of the newly developed self-bracketing search (SBS) classical dispersion (CD) analysis on published reflectance data of the internal modes of NaClO₃ indicates a plausible presence of anharmonic coupling in the v₁, v_3a,b region. The above SBS-CD analysis has also resulted in the evaluation of the dispersion parameter values for the internal modes of NaClO₃, and has provided the first quantitative determination of these values for the ³⁷Cl isotope.     

Characterization of silicon doped with sodium upon high-voltage implantation

The depth distribution profiles of sodium atoms in silicon upon high-voltage implantation (ion energy, 300 keV; implantation dose, 5 × 10¹⁴ and 3 × 10¹⁵ cm ^?2) are investigated before and after annealing at temperatures in the range T _ann = 300–900°C (t _ann = 30 min). Ion implantation is performed with the use of a high-resistivity p-Si (ρ= 3–5 kΩ cm) grown by floating-zone melting. After implantation, the depth distribution profiles are characterized by an intense tail attributed to the incorporation of sodium atoms into channels upon their scattering from displaced silicon atoms. At an implantation dose of 3 × 10¹⁵ ions/cm², which is higher than the amorphization threshold of silicon, a segregation peak is observed on the left slope of the diffusion profile in the vicinity of the maximum after annealing at a temperature T _ann = 600°C. At an implantation dose of 5 × 10¹⁴ ions/cm², which is insufficient for silicon amorphization, no similar peak is observed. Annealing at a temperature T _ann = 700°C leads to a shift of the profile toward the surface of the sample. Annealing performed at temperatures T _ann ≥ 800°C results in a considerable loss of sodium atoms due to their diffusion toward the surface of the sample and subsequent evaporation. After annealing, only a small number of implanted atoms that are located far from the region of the most severe damages remain electrically active. It is demonstrated that, owing to the larger distance between the diffusion source and the surface of the sample, the superficial density of electrically active atoms in the diffusion layer upon high-voltage implantation of sodium ions is almost one order of magnitude higher than the corresponding density observed upon low-voltage implantation (50–70 keV). In this case, the volume concentration of donors near the surface of the sample increases by a factor of 5–10. The measured values of the effective diffusion parameters of sodium at annealing temperatures in the range T _ann = 525–900°C are as follows: D ₀ = 0.018 cm²/s and E _a = 1.29 eV/kT. These parameters are almost identical to those previously obtained in the case of low-voltage implantation.     

Na+ ion conductivity and crystallographic cell characterization in the Hf-nasicon system Na1+xHf2SixP3−xO12

We have measured the effect of varying the mobile ion concentration on the sodium ion conductivity in the Hf-Nasicon system, Na_1+xHf₂Si_xP_3-xO₁₂, for 1.4 ? x ? 2.8. The conductivity is greatest for Na_3.2Hf₂Si_2.2 P_0.8O₁₂: σ_25°C = 2.3 × 10^?3 (ω cm)^?1, and σ_250°C = 1.7 × 10^?1 (ω cm)^?1. These values are approximately 50% greater and worse, respectively, than the values reported for the best Zr-Nasicon. We have characterized the variation of lattice parameters with composition and found the behavior to be similar to that of Zr-Nasicon. A small distortion from rhombohedral to monoclinic symmetry occurs for compositions 1.8 ? x ? 2.2.     

Mößbauereffekt in Eisenstilben und FeCl2·H2O

Using Mößbauer effect measurements in the temperature range between 3 °K and 310 °K the magnetic fields at the nucleus in iron-stilbene, FeCl₂·H₂O and FeCl₃ are determined to beH _T=0=(250±10) kOe, (252±18) kOe and (468±10) kOe; a Néel-temperature ofT _N=(23±1) °K is measured for iron-stilbene. The electric quadrupole splittings atT=0 °K for iron-stilbene and FeCl₂ ·H ₂ O, ΔE=(+2.52±0.02) mm/sec and (+2.50±0.05) mm/sec, yield electric field gradients at the iron nucleus ofq _z=+9.7·10¹⁷ V/cm² and +9.6·10¹⁷ V/cm², whereq _z⊥H; Debyetemperatures of θ=162 °K and 188 °K are obtained. The energy of the excited 3d-electron levels in iron-stilbene is estimated to Δ₁=309 cm^?1 and Δ₂=618cm^?1 as deduced from the temperature dependence ofΔE. In contrast to the suggestion ofEuler andWillstaedt bivalence of the iron in ironstilbene is found; its composition is shown to be 4(FeCl₂ ·H ₂O)·stilbene.     

Temperature dependence of the soft acoustic shear modes in h.c.p. zirconium

Neutron measurements of the dispersion curve v(q) for [10·0] phonons polarized in [11·0] are presented for hexagonal close-packed Zr at 300°, 773°, and 1073°K. Given that the crystal transforms to b.c.c. at 1135°K and demonstrates a pronounced softening in the C₆₆ elastic constant, v(q) shows only a uniform lowering of the entire branch, consistent with the behavior of C₆₆(T) but fractionally smaller for large wave vectors. No anomalous phonon linewidths are observed.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Study of the semi-conducting properties of pyrolusite

The electrical conductivity σ of the specimens is found to obey a relation of the type σ=C exp (?B/k T) over a temperature range 300 to 500° K whereC andB are constants. The experimentally determined values ofB and C are (1)B≈1490 to 2199 (2)C ≈ 0·72 × 10^?3 to 4·9 × 10^?3 ohms^?1 cms^?1. The value of the activation energy determined from the values ofB are ≈0·13 to 0·19 e.V. In A.C measurements σ is found to vary with voltage applied across the specimen at a given temperature. The i?V characteristics of metal point semi-conductor contacts are non-linear symmetrical curves and are strongly temperature dependant. The value of the Hall constant (?0·14 cm³/coul) yields carrier concentration as 4·3 × 10¹⁹/cm³, and mobility 1·2 cm² volt^?1 second^?1. Δ?/? for the specimen is found to vary asH ² where ? is the resistivity andH the value of magnetic field. The specimens develop a thermo-electric power of magnitude 200 μV/K to 500 μV/K which is fairly constant over the temperature range 300 to 800° K. The sign of the thermo-e.m.f. and of the Hall constant indicate that the specimens are “n” type.     

Absolute intensities and pressure broadening coefficients measured at different temperatures for the 201II ← 000 band of 12C16O2 at 4978cm-1

Absolute line intensities and self-broadening coefficients have been measured at 197° and 294°K for the 201_II ← 000 band of ¹²C¹⁶O₂ at about 4978cm^-1. The vibration-rotation factor (F_VR), the purely vibrational transition moment (∣R(O)∣), and the integrated band intensity (S_band) are deduced from the measurements. The results are: F_VR(m)=1+(0.24±0.08)x10^-4m+(0.55+0.21)x10^-4m², ∣R(O)∣= (4.340±0.008x10^-3 debye, S_band=96372±190cm^-1km^-1atm^-1_STP. The results for self-broadening coefficients, as well as for individual vibration-rotation lines, are presented in the text.     

EPR of cadmium ferric voltaite above the ferrimagnetic transition

A single isotropic EPR line of Fe³⁺ in synthetic cadmium ferric voltaite, (NH₄)₂Cd₅Fe₃Al(SO₄)₁₂ · 18H₂O, was observed in a wide temperature range from 295 to 1.57°K. The ferrimagnetic transition temperature of CdFe voltaite was determined to be ～ 0.7°K using the temperature dependence of the g-factor and the line width. The cubic crystal field parameter, a, for Fe³⁺ in CdFe voltaite is extracted from the EPR line width measurement using the exchange-narrowed line width model of Anderson and Weiss. The parameter a for Fe³⁺ in CdFe voltaite at 4.2°K is 157 × 10^-4cm^-1 which is consistent with the corresponding values for Fe³⁺ in other cubic structures.     

Indirect electronic transitions in alkali halate crystals-II (sodium bromate and iodate) crystals

In the case of NaClO₃ and KClO₃ crystals, analysis of the long wavelength tail of their fundamental absorption revealed the active participation of the internal vibrations of the chlorate ion (Part I). In order to test the validity of the above interpretation the absorption spectra of two more halates with different anions namely sodium bromate and sodium iodate are analysed in a manner similar to that given in Part I. It is found that the principle internal vibrations of bromate and iodate ions are involved in the indirect transitions. The variation of indirect band gap with temperature is found to be ?2·5 × 10^?4 eV/K and ?2·9 × 10^?4 eV/K for sodium bromate and sodium iodate respectively.     

Paramagnetische Resonanz von Er3+ in Y2O3

The paramagnetic resonance absorption of trivalent erbium in single crystals of Y₂O₃ on sites of crystal field symmetry C_3i and C₂ is investigated at 4.2°K and 9.2 kMc/s. The values of theg-tensors and those of the hyperfine structure parallel to the axes of crystalline fields are:g _‖=12.176,g _⊥=3.319,A=426.4·10^?4 cm^?1, andg _z =12.314,g _x =1.645,g _y =4.892, andA _z =433.2·10^?4 cm^?1 for the C_3i-ions and the C₂-ions, respectively. For ions on sites of symmetry C₂ the principal axes ofg in the plane perpendicular toz are found ± 2° beside the [100]-directions. This is different from the result on Yb³⁺ in Y₂O₃. The dependency ofg on the angle of rotation is determined for the (001)-, (110)-, and (111)-plane.     

Intensity and half-width measurements in the 1·525 μm band of acetylene

Line intensities at 150°K and 295°K, self-broadened half-widths at 171°K, 200°K, 250°K and 295°K, and hydrogen-broadened half-widths at 171°K, 200°K and 295°K have been measured in the ν₁+v₃ band of C₂H₂ at 1·525 μm. The absolute intensity of the band has been determined independently by employing the Wilson-Wells-Penner-Weber technique. Our best estimate for the absolute intensity of the band is S_v=7·82 ± 0·07 cm^?2 atm^?1 at 295°K. Line intensities calculated using this value of S_v are in good agreement with the measured intensities at the two extreme temperatures of 150°K and 295°K considered in the present study, thereby not suggesting any significant intensity anomalies. Line positions have been measured for the first time for this band for R(29)?P(25).     

Hall effect and magnetoresistance of (SN)x films

Hall effect and electrical conductivity have been investigated between 77 K and 300 K and the magnetoresistance at 4.2 K for a number of (SN)_x films deposited at substrate temperatures between — 10 and 50°C. The small magnitude of the Hall mobility (? 1 cm² Vsec^?1 at 300 K) and its activated temperature dependence are interpreted in terms of a heterogenous model for (SN)_x films with thin depletion layers separating highly conductive islands. The hole concentration in these islands (p ≈ 10²¹ cm^?3, the microscopic mobility (μ ≈ 500 cm² Vsec^?1 at 4.2 K) and the temperatures dependence of μ are found to be close to values for (SN)_x crystals.