Biasing effects on thallium and silver chlorides with dc/ac voltage

Comparison was made between crystals of thallium chloride and silver chloride on their biasing effects with dc/ac voltage. Previous reports say that, although their electrical conductivities are similar, the dominant charge carriers in the former are the Cl⁻ ions while the Ag⁺ ions in the latter. The present dc/ac study demonstrates the following: for thallium chloride, although Cl⁻ conduction may be dominant under low bias field, Tl⁺ conduction supercedes Cl⁻ conduction when the bias field is enhanced. For silver chloride, Ag⁺ conduction is overwhelming within wide temperature range, to cause easy dielectric breakdown on dc biasing. Concerning the extrinsic conductivity seen at temperatures below 60 °C (thallium chloride) or below 150 °C (silver chloride), it is ascribed to grain-boundary related electron conduction, not to grain-boundary related Tl⁺ or Ag⁺ conduction as reported earlier.     

Anomalous diffusion in presence of twin boundaries

After implantation of the ⁷¹Ge radiotracer in the Mg-1.8 wt% Al magnesium alloy, tracer diffusion coefficients were measured using both the serial sectioning and the residual activity technique in the temperature range from 448 to 848 K. Anomalously high diffusivities were observed at high temperatures where volume diffusion usually predominates. A contribution of high diffusivity paths to the total diffusion flux can be a possible explanation of both phenomena. Based on the high fraction of twin boundaries confirmed by electron microscopy, a simple microstructure model is proposed.     

Diffusion in nanocrystalline material

The paper reports on first investigations of the diffusion in nanocrystalline materials. The self-diffusion of the radioisotope ⁶⁷Cu in nanocrystalline copper has been measured by serial sectioning with the aid of ion-beam sputtering. The values of the diffusion coefficients which were found at 353 K and 393 K are 2×10⁻¹⁸ m²/s and 1.7×10⁻¹⁷ m²/s, respectively, i.e., they are about 16 or 14 orders of magnitude larger than the bulk self-diffusion and about 3 orders of magnitude larger than the grain-boundary self-diffusion in copper. In comparison to the bulk, small values for the activation enthalpy, 0.64 eV, and the pre-exponential factor of the self-diffusion coefficient, 3×10⁻⁹ m²/s, have been observed.     

Diffusion of gold in silicon studied by means of neutron-activation analysis and spreading-resistance measurements

In- and out-diffusion of gold in silicon were investigated with the aid of a neutronactivation analysis in combination with mechanical sectioning or by the spreadingresistance technique. In-diffusion profiles in the range 1371–1073 K show that Au diffuses in Si mainly via the so-called kick-out mechanism. From the Au diffusion and solubility measurements the interstitialcy contributionD _I ^SD to the Si self-diffusion coefficient was determined, which shows that the self-diffusion occurs to a considerable extent via selfinterstitials. Out-diffusion profiles at 1173 K were measured on wafers homogeneously supersaturated with Au. The observed decrease of the electrical activity of Au in the bulk indicates that during the out-diffusion anneal the majority of Au atoms originally dissolved substitutionally changes its configuration.     

A sectioning technique for sodium chloride single crystals and its application for ion implantation studies

A sectioning technique for sodium chloride single crystals has been developed. This technique, which is based on the formation of a silver chloride film, is capable of removing layers of constant thickness up to 2μg/cm². Being insensitive to radiation damage of the. NaCl-surface this film technique can be applied in studies of penetration and diffusion in NaCl. An electro-magnetic isotope separator has been used to implant radioactive phosphorous, krypton and xenon atoms in single crystals of sodium chloride, and examples are shown where the film technique has been applied for the study of range distributions and diffusion processes.     

Activation energy of self-diffusion along symmetric tilt grain boundaries 〈111〉 in the Ni3Al intermetallic compound

Activation energy of self-diffusion along symmetric tilt grain boundaries 〈111〉 in the Ni₃Al inter-metallic compound has been calculated depending on the temperature and misorientation angle. For comparison, two types of potentials of interatomic interaction have been used: pair Morse potentials and multi-particle Cleri-Rosato potentials. It has been shown that the activation energy of grain-boundary diffusion increases with temperature on applying the additional diffusion mechanisms. Three temperature ranges with various activation energies have been found.     

Phase relations, ionic transport and diffusion in the alloys of Cu2S-Ag2S mixed conductors

Results are reported of the phase relations in the (Ag_x-δ/2Cu_1-x)₂ system, ionic conductivity, self-diffusion and chemical diffusion coefficients for the solid solutions as a function of the composition x, degree of non-stoichiometry δ, and temperature in the range 473 – 673 K. The extensions of the homogeneity regions for single-phases are determined. Total and partial ionic conductivity values are given for copper and silver ions for the solid solutions. Measurements of the self-diffusion coefficient and the correlation factors are reported. It is shown that for solid solutions that the chemical diffusion is well described in terms of the phenomenological theory of ionic transport in mixed ionic electronic conductors.     

Gold and platinum diffusion: The key to the understanding of intrinsic point defect behavior in silicon

The study of gold and platinum diffusion is found to allow the separate observation of the intrinsic point defects, i.e., of silicon self-interstitials and of vacancies. The diffusion of gold in float zone (FZ) silicon is found to be dominated by the kick-out mechanism for temperatures of 800° C and higher. The diffusion of platinum in FZ silicon is described by the kick-out mechanism for temperatures above approximately 900° C, whereas for temperatures below approximately 850° C the dissociative mechanism governs platinum diffusion. As a result of numerical simulations, we suggest a complete and consistent set of parameters which describes the diffusion of platinum in silicon in the temperature range from 700° C to 950° C and the diffusion of gold in the temperature range from 800° C to 1100° C. The generation or recombination of self-interstitials and vacancies is found to be ineffective at least below 850° C. The concentration of substitutional platinum is determined by the initial concentration of vacancies at diffusion temperatures below 850° C. Platinum diffusion below 850°C can be used to measure vacancy distributions in silicon quantitatively.     

Determination of the Oxygen Diffusion Coeficient in Polycrystalline Li-Ti Ferrites

Two independent methods, the isotope method based on nuclear microanalysis and the method based on measuring the electronic-conductivity activation energy, are used to determine the grain-boundary diffusion and volume diffusion of an oxygen isotope ¹⁸O in a polycrystalline lithium-titanium ferrite at the thermal annealing temperature 1073 K. A comparative analysis is conducted of the potential of the methods in studying oxygen diffusion in the material concerned. It is shown that the technique for obtaining the diffusion parameters from the electronic conductivity measurements allows a comparatively precise determination of both the volume and grain-boundary diffusion coefficients of oxygen in polycrystalline ferrites.     

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.     

The effect of duration of diffusion on Ag diffusion coefficients in YBa2Cu3O7

The Ag diffusion in superconducting YBa₂Cu₃O₇ (YBaCuO) ceramic has been studied over the duration of the diffusion range 5-24 h in the temperature range 700-850 °C by the energy-dispersive X-ray fluorescence (EDXRF) technique. For the excitation of silver atoms, an annular Am-241 radioisotope source (50 mCi) emitting 59.543 keV photons was used. The temperature dependences of silver diffusion coefficients in grains (D₁) and over the grain boundaries in the range 700-850 °C (D₂) are described by the relations D₁=1.4×10⁻² exp[−(1.18±0.10)/kT] and D₂=3.1×10⁻⁴ exp[−(0.87±0.10)/kT].     

Grain boundary deformation in Cd-Zn and Zn-Al alloys

Activation energies for creep have been measured on fine-grained and coarse-grained specimens of pure cadmium, zinc, and Cd-Zn and Zn-Al alloys in the temperature range (0·4–0·8)T _m. It is found that in the case of fine-grained specimens the activation energies for creep are equal to the activation energies for grain boundary diffusion in cadmium and zinc, and in the case of coarse-grained specimens — to that of volume self-diffusion.     

The influence of surface forces on shear-induced tracer diffusion in mono and bidisperse suspensions

The shear-induced self-diffusivity of tracer particles of radius a _t = λa in a suspension of particles having a radius, a , is calculated by Stokesian dynamics for different values of the size ratio, λ , both in 2 and 3 dimensions in the binary-collision regime. The self-diffusion is found to decrease strongly when the size ratio becomes quite different from unity. On the other hand, for the same average distance of contact between two spheres, the presence of a soft force always increases greatly the diffusion compared to the effect of a hard shell which is used to model the roughness. This is particularly true for tracer particles smaller than the bath particles, where the shear-induced diffusion can be increased by many order of magnitudes in the presence of a soft force. For suspensions of monodisperse particles we show that, for low volume fraction, the diffusion coefficient is much smaller than the one predicted by the binary collision model, due to the existence of a layered structure. On the contrary at higher volume fraction, many-body collisions strongly enhance the diffusion and it appears that the value of the diffusion is quite sensitive to the presence of clusters of particles which are themselves determined by the range of interparticle forces.     

Model of grain-boundary self-diffusion in α- and β-phases of titanium and zirconium

A model of the grain-boundary self-diffusion process in metals undergoing phase transitions in the solid state is proposed. The model is based on the ideas and approaches of the theory of nonequilibrium grain boundaries. It is shown that the range of application of basic relations of this theory can be extended, and they can be used to calculate the parameters of grain-boundary self-diffusion in high-temperature and low-temperature phases of metals with phase transition. Based on the constructed model, activation energies of grainboundary self-diffusion in titanium and zirconium are calculated, and their anomalously low values in the low-temperature phase are explained. The calculated activation energies of grain-boundary self-diffusion are in good agreement with experimental data.     

Generic van der Waals equation of state for polymers, modified free volume theory, and the self-diffusion coefficient of polymeric liquids

In this paper, a molecular theory of self-diffusion coefficient is developed for polymeric liquids (melts) on the basis of the integral equation theory for site-site pair correlation functions, the generic van der Waals equation of state, and the modified free volume theory of diffusion. The integral equations supply the pair correlation functions necessary for the generic van der Waals equation of state, which in turn makes it possible to calculate the self-diffusion coefficient on the basis of the modified free volume theory of diffusion. A random distribution is assumed for minimum free volumes for monomers along the chain in the melt. More specifically, a stretched exponential is taken for the distribution function. If the exponents of the distribution function for minimum free volumes for monomers are chosen suitably for linear polymer melts of N monomers, the N dependence of the self-diffusion coefficient is N⁻¹ for the small values of N, an exponent predicted by the Rouse theory, whereas in the range of 2.3?lnN?4.5 the N dependence smoothly crosses over to N⁻², which is reminiscent of the exponent by the reptation theory. However, for lnN?4.5 the N dependence of the self-diffusion coefficient differs from N⁻², but gives an N dependence, N^−2−δ(0<δ<1), consistent with experiment on polymer melts in the range. For polyethylene δ≈0.48 for the parameters chosen for the stretched exponential. Because the stretched exponential function contains undetermined parameters, the N dependence of diffusion becomes semiempirical, but once the parameters are chosen such that the N dependence of D can be successfully given for a polymer melt, the temperature dependence of the self-diffusion coefficient can be well predicted in comparison with experiment. The theory is satisfactorily tested against experimental and simulation data on the temperature dependence of D for polyethylene and polystyrene melts.     

Approaches to diffusion barrier creation and trench filling for copper interconnection formation

The technique of copper filling of trenches which is based on the effect of the melting temperature decrease, depending on film thickness reduction, has been proved and demonstrated experimentally. An approach to diffusion barrier creation is proposed. Ta-W-N amorphous alloy has been selected as the barrier material for copper. This barrier layer keeps its properties in the Cu/Ta-W-N/TiSi₂/Si structure up to 800 °C, and in the Cu/Ta-W-N/SiO₂ structure up to 850 °C. The temperature for copper filling of the trenches is shown to be significantly lower than the temperature of bulk copper melting, and to depend on the thickness of the film. It is determined that this effect is caused not only by the lowering of the phase changing temperature as a result of the thinning of the film, but also by the system tendency to optimize its form by the change in the ratio of the surface and volume energies. When the thickness is 50 nm the temperature of filling is 750 °C, when it is 100 nm – 850 °C. However, this temperature reduction is not enough for use of the presented approach in UVLI technology, and further development of this approach is required, including possible combination with other filling methods. PACS 66.30.Ny; 68.35.Rh; 68.60.Dv     

Tracer impurity diffusion in single-crystal rutile (TiO2−x)

By means of the radioactive-tracer sectioning technique, the tracer diffusion of the impurity ions, ⁴⁶Sc, ⁵¹Cr, ⁵⁴Mn, ⁵⁹Fe, ⁶⁰Co, ⁶³Ni and ⁹⁵Zr, in rutile single crystals was measured as functions of crystal orientation, temperature, oxygen partial pressure and Al impurity content. The diffusion coefficients are very sensitive to the electric charge of the impurity ions. Divalent impurities (e.g., Co and Ni) diffuse extremely rapidly in TiO₂, compared to cation self-diffusion, and exhibit an extreme anisotropy in diffusion behavior, divalent-impurity diffusion parallel to the c-axis is much larger than it is perpendicular to the c-axis. Trivalent impurity ions (Sc and Cr) and tetravalent impurity ions (Zr) diffuse similar to cation self-diffusion, both as functions of temperature and oxygen partial pressure. The divalent impurity ions Co and Ni apparently diffuse as interstitial ions along open channels parallel to the c-axis. The results suggest that Sc, Cr and Zr ions diffuse by an interstitialcy mechanism involving the simultaneous and cooperative migration of tetravalent interstitial titanium ions and the tracer-impurity ions. Iron ions diffuse both as divalent and as trivalent ions. The impurity diffusion as functions of oxygen partial pressure and Al-impurity content are consistent with calculations of point-defect concentrations in rutile.     

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)     

Diffusion of Al implanted into α-Hf studied by means of the nuclear resonance technique

The diffusion of Al in -Hf was studied in the 973–1298 K temperature range by using the nuclear resonance technique. The measurements show that the diffusion coefficient follows an Arrhenius behavior D(T)=D₀exp(-Q/RT), where D₀=(3±2)×10^-4 m²s^-l and Q=337±10 kJ/mol. The activation energy is typical of a substitutional mechanism of diffusion, as can be deduced from self-diffusion measurements. On the other hand, differences between the present and previous published results can be attributed to the different purity of the samples used in each experiment. PACS 66.30.-h; 66.30.Jt