Grain Boundary Diffusion and Linear and Non-Linear Segregation of Ag in Cu

Ag grain boundary (GB) diffusion was measured in the Cu-0.2at%Ag alloy in a wide temperature range from 473 to 970 K. The direct measurements of Ag GB diffusivity D ^alloy _gb under conditions of the Harrison C regime revealed that D ^alloy _gb is almost identical to D ^pure _gb determined earlier for Ag diffusion in high-purity Cu (Divinski, Lohmann, and Herzig, 2001). The penetration profiles determined in the Harrison B regime showed a complex, multi-stage shape. This diffusion behavior can be rationalized assuming that besides GBs significantly covered by segregated Ag atoms, some fraction of GBs remains almost free from Ag atoms in the studied temperature interval. The total amount of pure GBs drastically decreases with decreasing temperature. This hypothesis was proven by measurements of Ag GB diffusion in Cu near 5 bicrystals, which allowed us to analyze in detail the non-linear segregation of Ag in Cu GBs.     

Temperature and orientation dependences of the grain-boundary diffusion coefficient of antimony in copper bicrystals

An investigation is made of the diffusion of antimony through the bulk and along grain boundaries in copper bicrystals containing a symmetric 〈100〉 misorientation boundary with misorientation angles from 20 to 37.2°. The bicrystals are grown by the method of horizontal zone recrystallization. The temperature range for these studies is 480–580 °C, where the solubility of Sb in Cu is about 6 atomic % and practically temperature-independent. The concentration profiles are obtained by x-ray spectral microanalysis, and the grain-boundary diffusion parameters are computed by the method of Whipple and Suzuoka. The orientation dependence of the triple product P=sδD _b (where s is the segregation coefficient, δ the width of the grain boundary, and D _b the grain-boundary diffusion coefficient) is nonmonotonic, with a maximum for the special ∑5 misorientation boundary (36.9°). The effective activation energy for grain-boundary diffusion ranges from ∼70 kJ/mol for ∑5 to140 kJ/mol for general boundaries. Fiz. Tverd. Tela (St. Petersburg) 39, 1153–1157 (July 1997)     

Pre-exponential factor for non-isothermal crystallization of glassy Se85− x Te15Sb x (0 ≤ x ≤ 10) alloys

We report observations of the Meyer–Neldel rule for the non-isothermal crystallization of glassy Se_{85? x} Te₁₅Sb _x (x =?0, 2, 4, 6, 8, 10) alloys. We found a strong co-relation between the pre-exponential factor K ₀ of the rate constant K(T) for crystallization and the activation energy of crystallization E _c. This indicates the presence of a compensation effect for the non-isothermal crystallization process in this glassy system. The composition dependence of the crystallization temperature T _c and the activation energy for crystallization E _c is discussed.     

Grain Boundary Diffusion and Segregation in Interstitial Solid Solutions Based on BCC Transition Metals: Carbon in Niobium

Bulk and grain boundary (GB) diffusion of ¹⁴C in Nb has been studied by the radiotracer serial sectioning technique. B and C kinetic regimes were realized for GB diffusion in the temperature range from 800 to 1173 K. The values of P = sD _gb, D _gb and s follow the Arrhenius dependencies: P = 5.15 × 10^–15 exp[–(83.1 kJ/mol)/RT] m³/s (973–1173 K), D _gb = 2.3 × 10^–6 exp[–(133.0 kJ/mol)/RT] m²/s (800–950 K), and s = 4.7 exp[(49.9 kJ/mol)/RT].The increase in the GB diffusion compared with self-diffusion is very large despite the probable retardation effect due to the strong segregation.The results for GB diffusion of C in Nb as well as for other interstitial solutes (P, S) in bcc transition metals (- Fe, Mo) are discussed in the framework of the transition state theory. It is assumed that GB segregation decreases the energy of the ground state whereas the change in the diffusion mechanism (e.g. from vacancy to interstitial) leads to a strong decrease of the transition state energy. This change in the diffusion mechanism results in a fast GB diffusion of interstitial solutes in spite of their large tendency to segregate to GBs.     

Determination of kinetic transport coefficients for ions in air as functions of electric field and temperature

A method for determining the kinetic coefficients of ion transfer in gases, viz., mobility K and longitudinal (D _L) and transverse (D _T) diffusion coefficients, as functions of the electric field E and gas temperature T is described. The method is based on the measurement of the increments to the ion mobility coefficients as functions of the electric field at a parametrically specified temperature. The kinetic transport coefficients K(E, T) and D _{L, T}(E, T) are determined for positive ions of aniline, pyridine, benzene, orthotoluidine, dimethyl methyl phosphonate, N-methyl aniline, N,N-dimethyl aniline, N,N-diethyl aniline, and diphenyl amine (DPA) formed as a result of β-ionization in air.     

Correlation between the Soret coefficient and the static structure factor in a polymer blend

Mutual mass diffusion and thermal diffusion has been investigated in poly(dimethylsiloxane)/ poly(ethylmethylsiloxane) (PDMS/PEMS) polymer blends of equal weight fractions. Molar masses ranged from below 1 to over 20 kg/mol. Both the mutual mass (D) and the thermal diffusion (D_T) coefficient contain a thermally activated factor with an activation temperature of 1415 K. The molar mass dependence of D_T is due to an end-group effect of the local friction coefficient. The thermal diffusion coefficient in the limit of long chains and infinite temperature is D_T^0, = - 1.69×10^-7cm²(sK)^-1. The Soret coefficient S_T of blends far enough away from a critical point is proportional to the static structure factor S(q = 0).     

Al/Ti/4H-SiC Schottky barrier diodes with inhomogeneous barrier heights

This paper investigates the current-voltage (I-V) characteristics of Al/Ti/4H-SiC Schottky barrier diodes (SBDs) in the temperature range of 77 K-500 K,which shows that Al/Ti/4H-SiC SBDs have good rectifying behaviour.An abnormal behaviour,in which the zero bias barrier height decreases while the ideality factor increases with decreasing temperature (T),has been successfully interpreted by using thermionic emission theory with Gaussian distribution of the barrier heights due to the inhomogeneous barrier height at the Al/Ti/4H-SiC interface.The effective Richardson constant A =154 A/cm 2 · K 2 is determined by means of a modified Richardson plot ln(I 0 /T 2)-(qσ) 2 /2(kT) 2 versus q/kT,which is very close to the theoretical value 146 A/cm 2 · K 2.     

Nuclear spin lattice relaxation and electric field gradient in liquid indium

We have measured the nuclear spin lattice relaxation time in liquid indium from 130°C to 300°C to be: 1/T ₁=(1.98 × 0.0082T) × 10³ sec^-1. The relaxation rate consists of two significant parts: (1/T ₁) _K from the nuclear magnetic hyperfine interaction, and (1/T ₁) _Q from the nuclear quadrupole interaction. We calculate (1/T ₁) _K from the the modified Korringa relation using a correction factor of order unity for electron-electron interactions. The hyperfine term is linear in T and accounts for the second term in 1/T ₁. Within experimental error the remaining rate, (1/T ₁) _Q , is temperature independent, and theoretically varies as the product of the square of the electric field gradient, q, and τ_c, a typical time between field gradient fluctuations. Making use of the x-ray RDF, we construct a simple model for liquid indium and calculate the ionic and electronic contributions, q _I and q _E, to the electric field gradient, to be q _I=1.4 × 10²⁴/cm³ and q _E=8.5 × 10²⁴/cm³. The calculation of q _E assumes covalent bonding between nearest neighbours. Taking q _I and q _E to be of opposite sign, we find that the correlation time τ_c is 1.6 × 10^-13 sec. When we further identify τ _c with the correlation time for diffusion in a three-dimensional random walk, we are able to calculate the r.m.s. jump distance, Δr _D, involved in self-diffusion, Δr _D=0.38 Å. This value is consistent with the x-ray peak width of 0.38 Å which we used earlier to calculate the electric field gradient.     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Mechanisms of bulk diffusion at “high” and “low” temperatures

A phenomenological model has been proposed for bulk self-diffusion and diffusion of interstitial atoms in the ranges of high (T > T _D) and low (T < T _D) temperatures (where T _D is Debye temperature). It has been shown that the mechanisms of diffusion at high and low temperatures differ significantly. In the high-temperature range, the diffusion is provided by fluctuations, which can be described in terms of local melting, i.e., the formation of a “liquid diffusion channel.” In the low-temperature range, when melting for some reasons is hindered, the diffusion is due to the fluctuation formation of a “hollow diffusion channel.” The calculation of the activation energies of these processes in the case of self-diffusion agrees well with the experiment in the temperature range T > T _D and has demonstrated that the activation energy increases significantly at T < T _D. The calculation of the activation energy for diffusion of interstitial atoms in bcc metals agrees well with the experiment in the entire temperature range and provides an explanation of the decrease in the activation energy of diffusion at low temperatures.     

Size and interface effects on Curie temperature of perovskite ferroelectric nanosolids

A simple and unified model, without any adjustable parameter, is established for size effect on Curie temperature of low-dimensional ferroelectrics (thin films, nanowires and nanoparticles), T _c(D), where D denotes size of low-dimensional ferroelectrics. T _c(D) function is based on consideration on the size dependence of spontaneous polarization of low-dimensional ferroelectrics P _s(D), which is determined by the misfit strain at the ferroelectrics/substrate interface. It is shown that P _s(D) and T _c(D) functions decrease or increase when the misfit strain is tensile or compressive. The numerically predicted results are in agreement with the available experimental results of BaTiO₃ and PbTiO₃ nanoparticles and thin films.     

Surface superconductivity and twinning-plane superconductivity in aluminum

The critical supercooling field H _sc is measured in aluminum single crystals and twinned bicrystals in a temperature range slightly below T _c0 (T _c0 ? 0.055 K < T < T _c0), where T _c0 is the critical superconducting transition temperature. It is found that, even in this small temperature range, the H _sc(H _c) dependence, which is considered to be identical to the H _c3(H _c) dependence for single crystals, is substantially nonlinear. The H _sc(H _c) dependences of the twinned bicrystals and single crystals are shown to be significantly different. The qualitative features of the phase diagram of the twinned aluminum bicrystals coincide with those of the phase diagram of twinning-plane superconductivity obtained earlier for tin in [1]. These findings allow the conclusion that the phenomenon of twinning-plane superconductivity also exists in face-centered cubic crystal lattices.     

Correlation betweenT c and elastic constants of (La−M)2CuO4

By an ultrasonic method, we measured the elastic constants of polycrystalline La_1.85M_0.15CuO₄ withM=Ca, Ba, Sr. These materials show zero-resistance normal-superconductive transition temperatures of 19, 28, and 36K. VersusT _c , all the elastic stiffnesses-bulk modulus, Young modulus, shear modulus-increase. Derived from the elastic constants and average atomic volume, the Debye temperature increases linearly withT _c . In conventional BCS superconductors,T _c decreases with increasing _D .     

Electron mobility in compensated VPE GaAs films

Electron Hall mobilities were measured on a series of intentionally compensated vapor phase epitaxy (VPE) GaAs layers. Using Sn and Zn as dopants, compensation ratiosK=(N_D+N_A)/(N_D-N_A) as high as 50 were obtained. Already for samples with the lowestK values the 300 K mobilities are higher than the 77 K values. In the range 20<T<100 [K] the data may be represented by μ∼T ^α with α increasing from 0.6 to 1.1 with compensation. The experimental μ values are smaller than those predicted from current models in all cases. It appears that scattering at ionized impurities is the dominant process also at temperatures well above 77 K, and that this scattering process is quantitatively underestimated in current models.     

Application of Boltzmann Equation on Spin Diffusion of Ferromagnetic Superfluid <Superscript>3</Superscript>He: Near Critical Temperature

Different scattering processes of quasiparticles containing a binary process, a coalescence process and a decay process in transition probabilities are taken into account. In the meantime, interaction between Bogoliubov quasiparticles as well as that between normal and superfluid components (spin up-spin down quasiparticles) of ferromagnetic superfluid ³He-A ₁ are considered. Pfitzner procedure is used in the calculation of triplet and singlet quasiparticle scattering amplitude existing in transition probabilities of the collision integral of standard Boltzmann equation at melting pressure. Pfitzner procedure is extended beyond s-p approximation by adding higher angular momentum components. Then, using the results of Boltzmann equation and considering smallness of the gap close to T _c↑, the change of the spin diffusion coefficients tensor of the A ₁-phase of superfluid ³He close to critical temperature and melting pressure is calculated. Temperature dependence of the spin diffusion coefficient change, i.e., δD _xyxy /D⌈=(3/2)(δD _xzxz /D)⌉, is −0.71(1−(T/T _c↑))^1/2. It is also shown that interaction between normal and Bogoliubov quasiparticles (normal-superfluid components interaction) is very important to transport properties such as spin diffusion close to critical temperature. Furthermore, using s-p approximation, the prefactor of δD _xyxy /D is plotted in terms of pressure; hence, the pressure dependence of δD _xyxy /D is also determined.     

Static and Dynamic Electron Holography of Electrically Active Grain Boundaries in SrTiO3

The dynamics of electrostatic potential barriers at grain boundaries (GBs) in Nb-doped SrTiO₃ bicrystals is investigated using a unique combination of bulk and in-situ TEM electrical measurements across isolated GBs, coupled with electron holography under in-situ applied bias. The Nb bulk-doped bicrystals exhibit a positive GB potential that suppresses reversibly under applied bias greater than the nonlinearity threshold in the current-voltage curve. This suppression is interpreted as break-down of the potential barrier to current transport.The results on Nb bulk-doped bicrystals have been compared to those in which Mn has been added as a grain boundary specific dopant. This acceptor doping of the grain boundary causes an appreciable increase in the grain boundary resistance and extension of the nonlinear regime. A preliminary account of static electron holography shows a relatively flat potential profile across the GB, indicating probable compensation of donor states at the GB core with Mn-acceptors. Interestingly, the phase profile under applied bias in this case exhibits a reversible dip at the GB which is interpreted as an activation of GB trap states due to Mn-acceptor dopants trapping extra electrons (the majority charge carriers) at the GB core, inducing a negative GB potential, and diminishing current transport until the threshold bias is exceeded.The synergistic combination of nanoscale TEM measurements coupled with traditional macroscopic electrical measurements is emphasized.     

Volume and grain boundary diffusion of implanted 113Sn in aluminium

Volume and grain boundary diffusion of ¹¹³Sn in aluminium was investigated with the radiotracer method. The implantation technique was used for tracer deposition to avoid problems of tracer hold-up caused by the oxide layer always present on aluminium. The diffusion penetration was chosen large enough to permit serial sectioning of samples with the aid of a microtome.The temperature dependence of the volume diffusivity was determined as D(T)=4.54×10^–5×exp[–(114.5±1.2)kJmol^–1/RT] m ² s ^–1. This confirms previous measurements from our group which already showed that Sn is the fastest foreign metal diffusor so far investigated in aluminium.Grain boundary diffusion of ¹¹³Sn in Al polycrystals was measured in the type-B kinetic regime. The grain boundary diffusion product P=sD _gb (s=segregation factor, =grain boundary width, D _gb=grain boundary diffusivity) was found to be strongly affected by the impurity content of aluminium. For Al polycrystals of 99.9992% nominal purity we obtained P _5N(T)=1.08×10^–8exp [–(96.9±7.5) kJ mol^–1/RT] m³ s^–1 and for less pure Al polycrystals of 99.99% nominal purity P _4N(T)=3.0×10^–10 exp [–(90.1±4.2) kJ mol^–1/RT] m³ s^–1 was determined. The grain boundary diffusion product in the purer material is more than one order of magnitude higher than in the less pure material. Very likely this is an effect of co-segregation of non-diffusant impurities into the grain boundaries.     

Characterization of photovoltaic cells using the photothermal deflection spectroscopy

The equilibrium segregation coefficientK ₀ of the following impurities has been measured in high-purity tellurium: Ag, Al, As, Cr, Cu, Fe, In, Mn, Ni, Pb, Pd, Ti, V, and their diffusion coefficient in liquid tellurium determined at 550 °C.     

Self diffusion in liquid Na-K alloy

Self diffusion coefficients,D _i, in liquid Na-K alloy at 373 K have been computed in the linear trajectory approximation of Helfand, with square well as an attractive tail. From the computedD _Na andD _K, the mutual diffusion coefficient,D _NaK has also been determined.D _Na,D _K andD _NaK all increase with increase of concentration of potassium, while the ratio,D _Na/D _K remains constant (1.45 ± 0.01) over the entire concentration range.     

First principles calculations of alloying element diffusion coefficients in Ni using the five-frequency model

The diffusion coefficients of several alloying elements(Al,Mo,Co,Ta,Ru,W,Cr,Re) in Ni are directly calculated using the five-frequency model and the first principles density functional theory.The correlation factors provided by the five-frequency model are explicitly calculated.The calculated diffusion coefficients show their excellent agreement with the available experimental data.Both the diffusion pre-factor(D 0) and the activation energy(Q) of impurity diffusion are obtained.The diffusion coefficients above 700 K are sorted in the following order:DAl>DCr>DCo>DTa>DMo>DRu>DW>D Re.It is found that there is a positive correlation between the atomic radius of the solute and the jump energy of Ni that results in the rotation of the solute-vacancy pair(E 1).The value of E 2-E 1(E 2 is the solute diffusion energy) and the correlation factor each also show a positive correlation.The larger atoms in the same series have lower diffusion activation energies and faster diffusion coefficients.