Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Orientation-dependent mobilities from analyses of two-dimensional TiN(111) island decay kinetics

We present a method for the determination of orientation-dependent mobilities Γ_eff(φ) based upon analyses of the detachment-limited coarsening/decay kinetics of equilibrium-shaped two-dimensional islands. An exact analytical expression relating the orientation-dependence of Γ_eff(φ) to that of the anisotropic step energies β(φ) is derived. This provides relative values of Γ_eff(φ) to within an orientation-independent scale factor that is proportional to the decay rate of the island area. Using in situ high temperature (T = 1550–1700 K) low-energy electron microscopy measurements of two-dimensional TiN island coarsening/decay kinetics on TiN(111) terraces for which β(φ) values are known [Phys. Rev. B 67 (2003) 35409], we demonstrate the applicability of our analytic formulation for the determination of absolute Γ_eff(φ) values.     

Electrochromic properties of nanocrystalline MoO3 thin films

Electrochromic MoO₃ thin films were prepared by a sol–gel spin-coating technique. The spin-coated films were initially amorphous; they were calcined, producing nanocrystalline MoO₃ thin films. The effects of annealing temperatures ranging from 100 °C to 500 °C were investigated. The electrochemical and electrochromic properties of the films were measured by cyclic voltammetry and by in-situ optical transmittance techniques in 1 M LiClO₄/propylene carbonate electrolyte. Experimental results showed that the transmittance of MoO₃ thin films heat-treated at 350 °C varied from 80% to 35% at λ = 550 nm (ΔT =  45%) and from 86% to 21% at λ ≥ 700 nm (ΔT =  65%) after coloration. Films heat-treated at 350 °C exhibited the best electrochromic properties in the present study.     

First principles calculations of thermal equations of state and thermodynamical properties of MgH2 at finite temperatures

We present the first principles calculations of the thermodynamical properties of magnesium hydride (MgH₂) over a temperature range of 0–1000 K. The phonon dispersions are determined within the density functional framework and are used to calculate the free energy of MgH₂ within the quasiharmonic approximation (QHA) at each cell volume and temperature T. Using the free energies the thermal equation of state (EOS) is derived at several temperatures. From the thermal EOS structural parameters such as the equilibrium cell volume (V₀) and elastic properties, namely, bulk modulus (K₀) and its pressure derivative are computed. The free energies are also used to calculate various thermodynamical properties within QHA. These include internal energy E, entropy S, specific heat capacity at constant pressure C_P, thermal pressure P_thermal(V, T) and volume thermal expansion ΔV/V (%). The good agreement of calculated values of S and C_P with experimental data exhibits that QHA can be used as a tool for calculating the thermodynamical properties of MgH₂ over a wide temperature range. P_thermal(V,T) increases strongly with T at all the volumes but it is a slowly varying function of volume for T = 298–500 K. According to Karki [B.B. Karki, Am. Miner. 85 (2000) 1447] such volume based variations can be neglected and so it is possible to estimate the thermal EOS only with the knowledge of the measured P_thermal(V, T) versus temperature at ambient pressure and isothermal compression data at ambient temperature. Temperature dependence of ΔV/V(%) shows that V₀ increased with increase in temperature. However, the percentage decrease in K₀ superseded this percentage increase in V₀ even at temperatures moderately higher than 298 K. Therefore, we suggest application of temperature (T > 298 K) as an approach to enhance the hydrogen storage capacity of MgH₂ because of its better compressibility at these temperatures.     

Effect of ferroic domain pattern changes on the Raman spectra of some ferroic crystals

The influence of changes in the pattern of ferroic domain structure on the Raman spectra of β-LiNH₄SO₄ and (NH₄)₃H(SO₄)₂ single crystals were studied. It was shown that the Raman spectra of β-LiNH₄SO₄ passed from the ferroelastic phase differ from those of “as-grown” crystal and those of the crystal, which was in the paraelectric phase. Significant changes could be observed in the Raman bands related to triply degenerated ν₃ and ν₄ vibrations of the SO₄ tetrahedron. Detailed temperature studies of the Raman spectra of β-LiNH₄SO₄ close to the paraelectric–ferroelectric phase transition, exhibit anomaly of some internal vibrations of SO₄ in the temperature range where a regular large-scale structure is observed. Different types of evolution of the ferroelastic domain structure and temperature behaviour of the donor and acceptor vibrations were shown while heating and cooling the (NH₄)₃H(SO₄)₂ crystal. Different values of temperature hysteresis were found in temperature studies of the ferroelastic domain structure (ΔT_S  3–5 K) and in Raman spectra studies (ΔT_S  12 K). No changes were observed in the pattern of ferroelastic domain structure at the temperature T_II–III  265 K, at which C2/c → P2/n structural phase transition takes place. On the other hand, at T_III–IV  135 K additional domains with W′-type of domain wall orientation were found.     

The effect of heat treatment on the microstructure stability of modified 316LN stainless steel

As a conduit-sheath material for Cu–Nb–Sn wires, chemically modified 316LN steel is subjected to the same reaction heat treatment (100 h at 700 °C) used in transforming the wires into superconducting composite wires. In spite of the long annealing time at 700 °C, there was little or no change in the strength of the steel. A systematic study of the material annealed for 1, 10, 20, 50 and 100 h using orientation imaging microscopy (OIM) showed that with the exception of grain boundary precipitation at t = 100 h, the grain size and grain boundary character were stable. Our results show that twin boundaries (Σ3, Σ9, and Σ27) accounted for about 50% of the total boundaries in all the material conditions studied, suggestive that the density of twins had reached a limit. The stability of the material in spite of the prolonged heat treatment was attributed to the attainment of this maximum twin density in the as-received condition. In view of the high percentage of the twin boundaries in the microstructure, a comprehensive Hall–Petch relationship, which incorporates the contribution of the chemistry, grain size as well as twin boundaries to strengthening was developed. This upper bound theoretical strength compared favorably with the experimental value at 4 K.     

Formation of intermetallic compound layers in Sn/Au/Sn diffusion couple during annealing at 433 K

The kinetics of the reactive diffusion between Au and Sn was experimentally studied in a metallographical manner. Sn/Au/Sn diffusion couples were prepared by a solid-state diffusion bonding technique and then annealed at 433 K for various times between 1 and 127 h (3.6 × 10³ and 4.57 × 10⁵ s) in an oil bath with silicone oil. Due to annealing, intermetallic compound layers consisting of AuSn₄, AuSn₂ and AuSn are produced at the Au/Sn interface in the diffusion couple. The thickness of the AuSn₄ layer is four times greater than those of the AuSn₂ and AuSn layers. The ratio of the thicknesses of the compound layers remains constant during annealing. The total thickness l of the compound layers increases with annealing time t. Such a relationship is mathematically described by the equation l = k(t/t ₀)ⁿ, where t ₀ is unity time, 1 s. From the experimental results, the proportionality coefficient and the exponent are determined to be k = 2.7 × 10^–7 m and n = 0.42, respectively, by a least-squares method. The exponent n is slightly smaller than 0.5. This implies that the grain boundary diffusion partially contributes to the rate-controlling process for the growth of the compound layers.     

Perpendicular Magnetic Tunnel Junctions with CoFe/Pd Multilayer Electrodes and an MgO Barrier

We studied the magnetic and magnetoresistance characteristics of pseudospin-valve magnetic tunnel junctions (MTJs) based on CoFe/Pd multilayer electrodes with perpendicular magnetic anisotropy and an MgO barrier. The MTJs at annealing temperature (T _a) of 473 K showed a tunnel-magnetoresistance (TMR) ratio of 1.5%. An fcc (111)-oriented texture of the bottom and top Co₉₀Fe₁₀/Pd multilayer electrodes, together with an imperfectly crystallized MgO, were revealed by cross-sectional TEM images. The TMR properties of perpendicular MTJs with a Co₂₀Fe₆₀B₂₀ or Co₅₀Fe₅₀ layer inserted between the CoFe/Pd multilayer electrodes and the MgO barrier were also studied. The TMR ratio with Co₂₀Fe₆₀B₂₀ insertion was 1.7% at T _a= 473 K and monotonically decreased at T _a over 523 K. The TMR ratio with Co₅₀Fe₅₀ insertion increased up to 3% at T _a= 573 K and then decreased to 0.4% at T _a= 598 K. The influence of the Pd layer on CoFeB was studied by using the simplified structures of Pd/CoFeB/MgO/CoFeB/Pd and Ta/CoFeB/MgO/CoFeB/Ta with inplane anisotropy. A former structure with Pd resulted in reduced TMR ratio which decreases with increasing T _a, whereas MTJs with a Ta-based structure showed a monotonic increase of a TMR ratio. The low TMR ratio observed in Pd-containing structures appears to result from crystallization of CoFeB in an unfavorable crystal orientation.     

YNixMn1−xO3 thin films by pulsed laser deposition: Structure and magnetic properties

Highly oriented YNi_xMn_1−xO₃ thin films on SrTiO₃ (100) substrates were achieved by using pulsed laser deposition for x = 0.33 and x = 0.50. We used a combination of X-ray diffraction, scanning electron microscopy, atomic force microscopy, and magnetic-property measurements. The magnetic transition temperatures (T_c) of the as-grown films are higher than the corresponding bulk values (typically 85 K instead of 80 K, for x = 0.5, and 60 K instead of 50 K, for x = 0.33). Our magnetic measurements also suggest a spin-glass characteristic in the x = 0.33 films, while a cluster glasslike behavior is observed for the films with x = 0.5, which is quite different from that of the bulk samples. Finally, the influence of post-deposition heat treatment on the magnetic properties of the as-grown films is discussed.     

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.     

CdGeAs2晶体的热膨胀行为研究

采用WinTA 100热膨胀仪研究了四方黄铜矿CdGeAs₂晶体在320~620 K温度范围内的热膨胀行为, 探索了CdGeAs₂晶体热膨胀各向异性的物理机制。测定晶体a轴和c轴方向的热膨胀系数α_a和α_c发现, α_a>>α_c>0, 表现出强烈的各向异性热膨胀特性。利用最小二乘法, 拟合出CdGeAs₂晶体的晶格常数(a, c)与温度(T)的函数关系式, 与文献报道值吻合。分别计算出不同温度下的四方畸变因子δ=2-c/a, Cd-As 键长(l_Cd-As)和 Ge-As 键长(l_Ge-As)以及相应的热膨胀系数α_Cd-As和α_Ge-As。结果表明, a、c、δ、l_Cd-As、l_Ge-As和α_Cd-As均随着温度的升高而增大, c/a和α_Ge-As则随着温度的升高而减小。当T=360 K时,α_Cd-As是α_Ge-As的6.36倍, 是造成CdGeAs₂晶体强烈热膨胀各向异性的主要原因。     

Comparison of sensing characteristics of ChemFEC devices based on spin-coated thin films of calix[n]arenes

ChemFECs (chemical field effect capacitors) or EIS (Electrolyte-Insulator-Semiconductor) devices were coated with calix[n]arene macrocycles for cation sensors development. Silicon nitride surface electrodes were spin-coated with p-tert-butylcalix[n]arene molecules for n = 8, 9 and 11. Electrochemical capacitance measurements were carried out to evaluate the sensitivity of the calix[n]arene layers towards specific cations as calcium and copper ions. Sensor responses were due to the “host-guest” specific interaction between the rigid cavity of calix[n]arene receptors (ligand) and chemical ion species. The developed chemical sensors have demonstrated good analytical characteristic in terms of: stability, selectivity and lifetime. In addition, experimental results were fitted using the site binding model in order to determine complex association constants, pK (1.9 ≤ pK ≤ 6.39) and surface density of ligands, N_L (9.10¹⁴ ≤ N_L ≤ 2.10¹⁶). All results obtained in this work were compared with those obtained using silicon dioxide EIS electrodes coated with the same calix[n]arene receptors using both spin-coating and thermal evaporation deposit processes.     

Optical properties of Nd:NaLa (WO4)2 single crystal

Nd³⁺-doped NaLa(WO₄)₂ single crystal with a dimension of 20 mm × 40 mm and a good optical quality was grown by Czochralski method. The polarized absorption spectra and emission spectra were measured at room temperature. The absorption cross-section and emission cross-section were presented. The Judd–Ofelt theory, extended to anisotropic system, has been applied to evaluate the intensity parameters Ω_t (t = 2, 4, 6), radiative transition rates A, radiative lifetimes τ_R and fluorescent branching ratios β. The calculated radiative lifetime was compared with the experiment data for the ⁴F_3/2 emitting level. All spectral features are strongly affected by an inhomogeneous broadening connected with the ‘disordered crystal’ character of the title compound.     

Effect of Ni on reactive diffusion between Au and Sn at solid-state temperatures

Influence of Ni on the kinetics of the reactive diffusion between Au and Sn was experimentally studied at solid-state temperatures. Binary Sn–Ni alloys with Ni concentrations of 1, 3 and 5 mass% were used to prepare sandwich (Sn–Ni)/Au/(Sn–Ni) diffusion couples by a diffusion bonding technique. The diffusion couples were isothermally annealed at temperatures of T = 433, 453 and 473 K for various times in an oil bath with silicone oil. After annealing, AuNiSn₈, AuSn₄, AuSn₂ and AuSn compound layers were observed to form at the (Sn–Ni)/Au interface in the diffusion couple. The total thickness l of the compound layers monotonically increases with increasing annealing time t according to the equation l = k(t/t₀)ⁿ, where t₀ is unit time, 1 s. The exponent takes values between n = 0.29 and 0.37 under the present annealing conditions. Such values of n < 0.5 indicate that the grain boundary diffusion contributes to the rate-controlling process and the grain growth occurs at certain rates. The higher the Ni concentration of the Sn–Ni alloy is, the faster the overall growth of the compound layers occurs. This means that Ni is an accelerator for the reactive diffusion between Au and Sn at solid-state temperatures. The acceleration effect of Ni becomes more remarkable at higher annealing temperatures. Such influence of Ni on the kinetics is mainly attributed to the dependencies of the growth rate of the AuNiSn₈ layer on the composition of the Sn–Ni alloy and the annealing temperature.     

Synthesis and crystal structure of [2-NH2-5-CH3C5H4N]4P4O12·6H2O

Chemical preparation, crystal structure, IR absorption and thermal analysis of a new cyclotetraphosphate [2-NH₂-5-CH₃C₅H₄N]₄P₄O₁₂·6H₂O are reported. This compound is triclinic P-1 with unit-cell parameters: a = 10.206(5), b = 11.778(1), c = 9.991(4) Å,  = 110.40(6), β = 117.74(6), γ = 86.41(3)°, V = 989.1(8) Å³, Z = 1, D_x = 1.445 g cm⁻³. The structure has been determined and refined to R = 0.034 and R_w = 0.044, using 3663 independent reflections. The ring anions and water molecules form layers spreading around (a, b + c) planes via OHO hydrogen bonds. Between them are anchored 2-amino-5-methylpyridium cations, which establish H-bonds to interconnect the different adjacent layers and so contribute to the cohesion of the three-dimensional network. Tautomerization of (C₆H₉N₂)⁺ groups was evidenced in the present structure.     

Growth kinetics of Mo3Si layer in the Mo5Si3/Mo diffusion couple

The diffusion processes and growth kinetics of the Mo₃Si silicide layer occurring at annealing the Mo₅Si₃/Mo diffusion couple between 1180 and 1800 °C were studied by electrothermography. The experimental results are supplemented with calculations on the behaviour of the initial Mo₅Si₃/Mo diffusion couple on the basis of the reaction diffusion model describing the transformation of the Mo₅Si₃ layer into a Mo₃Si one. The values of the parabolic growth constant for Mo₃Si layer were determined and the silicon diffusion coefficient in the Mo₃Si phase was calculated: D = 0.165 exp[(− 247 ± 10) / RT], cm²/s, where the activation energy is expressed in terms of kJ/mol.     

Correlation of structure and optical properties of an annealed hydrogenated amorphous silicon-carbon alloy film

A hydrogenated amorphous silicon-carbon (a-Si_0.76C_0.24:H) film has been prepared via the glow discharge decomposition of SiH₄ and C₂H₄. The optical constants of this alloy film have been determined as a function of annealing temperature T_a for photon energies between 1.5 and 4.75 eV. The refractive index n and its imaginary part k show small but significant variation with annealing temperature. The optical energy gap E_opt also exhibits interesting variation with annealing temperature, decreasing with increasing annealing temperature up to T_a = 650°C and then increasing above this temperature. Further, E_opt is found to be correlated with the inverse of the full width at half-maximum of the Si---C and the Si---O IR stretch absorption mode, which seems to indicate that the changes in E_opt are structural in origin and that phonon order correlates well with electronic order.     

Crystal structure and spectroscopic studies of NaGd(PO3)4

Single crystals of gadolinium–sodium polyphosphate NaGd(PO₃)₄ were grown for the first time using a flux method and characterized by X-ray diffraction. This phosphate crystallizes in a monoclinic system with P2₁/n space group and with the following unit-cell dimensions: a = 9.767(3) Å, b = 13.017(1) Å, c = 7.160(2) Å, β = 90.564(5)°, V = 910.3(4) Å³ and Z = 4. The crystal structure was solved from 3451 X-ray independent reflections with final R(F²) = 0.0219 and R_w(F²) = 0.056 refined with 164 parameters (). The atomic arrangement can be described as a long chain polyphosphate organization. Two infinite (PO₃)∝ chains with a period of eight tetrahedra run along the [0 1 1] direction. The structure of NaGd(PO₃)₄ consists of GdO₈ polyhedra sharing oxygen atoms with phosphoric group PO₄. Each Na⁺ ion is bonded to eight oxygen atoms.     

Synthesis and characterization of aromatic self-assembled monolayers containing methylene and ethyleneglycol entities by means of sum-frequency generation spectroscopy

We use infrared-visible sum-frequency generation (SFG) spectroscopy in order to investigate the adsorption properties on Pt(111) of molecules having CH₃–C₆H₄–(O–CH₂–CH₂)_n–O–(CH₂)_m–SH as general chemical formula. We synthesized three molecules defined by the values m = 5 n = 4, m = 11 n = 4, m = 11 n = 8 and characterized them by Nuclear Magnetic Resonance spectroscopy. Thanks to spectroscopic measurements, we show that these molecules build self-assembled monolayers on Pt(111). First, the weak SFG signals arising from the ad-layer indicate low order and surface coverage of the substrate by these molecules. Next, the vibrational fingerprints of the aforementioned molecules are determined between 2825 and 3125 cm^− 1 and the observed SFG spectral features are ascribed on the basis of the analysis of shorter and simpler molecules (1-dodecanethiol, 4-methylbenzenethiol and CH₃–C₆H₄–O–(CH₂)₁₁–SH) also adsorbed on Pt(111). The occurrence of methylene vibration modes indicates a significant amount of chain defects whatever the n and m numbers are. Finally, the identification of a particular vibration mode, characteristic of the aromatic ring, enables us to qualitatively discuss the effect of the number of methylene and ethylene glycol entities on its orientation. More precisely, higher these numbers, more tilted (with respect to the substrate normal) the aromatic ring plane is.     

Thermally stable Pd/Sn and Pd/Sn/Au ohmic contacts to n-type GaAs

Thermal stability of novel Pd/Sn and Pd/Sn/Au Ohmic contacts to n-GaAs has been investigated and compared to the non-alloyed Pd/Ge and alloyed Au–Ge/Ni metallizations. Metallization samples are furnace annealed at various temperatures and systematically characterized utilizing Scanning Electron Microscopy (SEM) and current–voltage (I–V) measurements. Contact resistivities, ρ_c, of the proposed metallization are measured using a conventional Transmission Line Model (cTLM) method. The Pd/Sn Ohmic contacts display superior thermal stability at 410°C when compared to the Pd/Ge contacts. After annealing at 410°C for 4 h, ρ_c of the Pd(50 nm)/Sn(125 nm) metallization remains in the low 10⁻⁵ Ω cm² range, whereas ρ_c values increase to 10⁻⁴ Ω cm² for the Pd(50 nm)/Ge(126 nm) contacts. At 410°C, the Pd/Sn/Au metallizations also display better thermal stability than that of non-alloyed Pd/Ge and alloyed Au–Ge/Ni metallizations. The long-term stability at 300°C of the Pd/Sn and Pd/Sn/Au Ohmic contacts is also reported.