Surface self-diffusion studied by microscopic measurements of crystallite profile evolutions

Dendritic gold crystallites on graphite are heated in ultra high vacuum up to less than 0.5 of the melting point (T_m). Electron microscopy shows that the gold crystallites change their shapes by surface self-diffusion. The dendritic contours round off while the crystallite remains very flat (20 to 40 Å). The increase with time of the radii of dendrite tips is measured statistically. Such an evolution can be described by analogy to the blunting of either metal tips (Nichols and Mullins) or monoatomic cleavage tips (Höche and Bethge). Using this result, a new technique to measure surface self-diffusion coefficients (D) is proposed. Test measurements have shown that this is an interesting, very sensitive method to measure D (down to 10^?13 cm^?2 s^?1) which enables measurements to be made in an unusual low temperature range (0.25 T_m < T < 0.5T_m). In special cases the dendrites are split by the surface self-diffusion which is qualitatively in agreement wih the theory.     

The effective activation energy Ueff(T,B,J) in Hg-1223 single phase superconductors

We review the methods of calculating the effective activation energy U_eff(T,B,J) for both transport measurements and magnetic decay, together with some theoretical models. Then, we apply these methods to our Hg-1223 single-phase superconductor to obtain the activation energy. Transport results give that the magnetic field and temperature dependence of the U_eff can be well described as U₀B^−α(1−T/T_c)^m. Magnetic relaxation shows that the current density dependence of U(J) can be scaled onto a single curve, which can be considered as the activation energy at some temperature T₀. The pinning mechanism in the measured temperature range does not change, and the activation energy depends separately on the three variables: T, B, and J, are responsible for the magnetic decay data scaling onto a single curve at various temperatures. As temperatures close to zero and near T_c, thermally assisted flux motion model is no longer valid since other processes dominate.     

Dipolar dielectric relaxation in CeO2-YO1,5 solid solutions

The dielectric properties of yttrium oxide-doped cerium oxide solid solutions have been studied by using a.c. techniques. Frequency and temperature respectively range from 10 to 10⁵ Hz and from 70 to 200°C. Both a complex impedance plot (Z″ vs Z′) and a conductance plot (G at fixed frequency vs inverse of temperature T^?1) are shown to be complementary for an accurate determination of the bulk resistance and of the dielectric loss. For the three investigated concentrations of yttrium oxide (m/% YO_1,5:0.001, 0.01 and 0.1), the activation energies for conduction are equal to 0.86, 0.75 and 0.75 eV, while the activation energy for dipole reorientation is found to be concentration independent (0.75 eV; angular frequency preexponential factor: 6.0 × 10¹², 1.43 × 10¹³ and 3.05 × 10¹³ s^?1). Moreover, the dipolar relaxation rates are found to be of the same order of magnitude as that of the migration rate. Interpretation is given on the basis of Wachtman's model and of previous results obtained by Nowick et al. from ITC (ionic thermo-current) investigations. The observed dielectric peak appears to be due to the redistribution of oxyygen vacancies between charged (Y_Ce-V₀) pairs and fixed charged Y_Ce defects.     

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.     

代位合金中的空穴扩散和有序化

本文根据空穴扩散促使有序化的观点导出决定恒温有序化几率的一个公式。这个公式中包括扩散系数,柯诺库夫温度及其他实验都可以直接测定的数量。引用了现有的这些数量的实验数据,证明所提出的有序化几率公式和实验结果是符合的。     

Vacancy-induced heat transfer in solid Kr and Ar

We have measured constant-volume thermal conductivities of solid krypton at six molar volumes between 28.84 and 29.54 cm³ mole^?1 and of solid argon at a molar volume of 24.30 cm³ mole^?1 at temperatures of order and above the respective Debye temperatures. An excess thermal conductivity above that following from the T^? law is ascribed to an additional energy flux carried over by vacancies. The estimated activation energy Q_P for self-diffusion derived from the constant-volume values Q_V as determined from the temperature dependences of the “excess” thermal conductivities are in good agreement with the available data of direct diffusion measurements in solid Ar and Kr.     

Ion bombardment induced phase transformations and inert gas mobility in the semiconductors Ge,Si, and GaAs

Abstract

The present study contributes some new aspects to the general understanding of the ion implantation behaviour of 3 common semiconductor materials, and of diffusion processes in these materials. Single crystals of Si, Ge, and GaAs were bombarded with Kr- or Xe-ions at energies of 40 or 500 keV and doses between 10¹¹ and 2 × 10¹⁶ ions/cm². Gas release measurements and Rutherford scattering of 1 MeV He⁺-ions combined with channeling were used to study bombardment damage (amorphization) and inert gas diffusion. At low bombardment doses (10¹¹ ions/cm²) and energy (40 keV), no damage was observed and the gas release was compatible with volume diffusion resembling Group I and VIII behaviour. Hence, the pre-exponential terms, D ₀, were low (range 10-^5±1 cm² sec^?1) and the activation enthalpies, Δ H, were much lower than those of self-diffusion or of diffusion of Group III and V elements. The Δ H's for gas diffusion followed the relation Δ H = (1.05±0.1) × 10^?3 T_m eV with the melting point, T_m , in °K. The mechanism of gas mobility might be the Turnbull dissociative mechanism. Rutherford scattering and channeling data indicated that part of the gas occupied lattice sites.

At higher doses, the bombarded layers turned amorphous. Channeling experiments showed a coincidence in temperatures for a gas release process different from the above one of volume diffusion, and recrystallization of the disordered layer to the single crystalline state. Both processes occurred in the temperature range 0.60 to 0.65 T_m . The gas release indicated a (partial) single jump character with implied Δ H's following the relation Δ H = (2.1±0.1) × 10^?3 T_m eV. Contrary to previous results on oxides, this new gas release occurred at temperatures near to those or even above those of volume diffusion of the gas.

Due to the easy formation of an amorphous layer it was difficult to observe the retarded release (trapping of gas) that has been found in many materials at high gas and damage concentrations. However, in a separate series of experiments with 500 keV Kr-ions, a release retarded with respect to volume diffusion of the gas was observed in Si and Ge.     

Deep levels in gallium arsenide by capacitance methods

The three capacitance methods, i.e., TSCAP, PHCAP, and transient capacitance measurements, are applied to determine electronic properties of deep levels inn-GaAs. In the boat-grown wafer detected are the 0.30 eV electron trap withN _T =3.6×10¹⁶ cm^?3 andS _n =2.4×10^?15 cm², and the 0.75 eV electron trap withN _T =2.0×10¹⁶ cm^?3 andS _n =1.2×10^?14 cm². In the epitaxial wafer, the 0.45 eV hole trap is detected withN _T >1.5×10¹³ cm^?3 andS _p =1.4×10^?14 cm² as well as the 0.75 eV electron trap withN _T =2.4×10¹³ cm^?3.     

Electrical conduction and 1ƒ noise in Li-DOPED MnO

Electrical resistivity, thermoelectric power and current noise were measured on Li-doped MnO single crystals in the temperature range from 300 to 1000 K. Below 700 K the crystals are p-type and the activation energy of the resistivity is 0.75 eV. Around 700 K the activation energy changes from 0.75 to 1.25 eV owing to a change from p- to n-type conduction. The depth of the Li acceptor is found to be 0.65 eV. From resistivity and thermoelectric power data it is concluded that the bandgap in first approximation can be written as E_s(T) = E_o ? γT between 750 and 1000 K, with E_o = 1.9 eV and γ = 6 × 10^?4 eV/K. The current noise spectra show $\text{1}\text{?}$ noise. The magnitude of the $\text{1}\text{?}$ noise is strongly temperature dependent. From the noise data it is deduced that E_o = 2.2 eV and γ = 10^?3 eV/K in the temperature range 430–700 K.     

Surface energy anisotropy of tungsten

Field-ion microscopy was used to study the faceting behavior and/or surface energy anisotropy of tungsten in vacuum and in hydrogen. In vacuum below 1700 K the activation energy for {110} facet growth agreed with values previously reported for surface diffusion on tungsten. The observed anisotropy values at 0.5 T_m, where T_m is the absolute melting temperature of tungsten (～3680 K), were different from those previously reported at higher temperatures and more nearly agreed with broken bond calculations based on Mie potential using m = 5, n = 8, and a 1.5% lattice expansion. Hydrogen appeared to have a negligible effect on surface energy anisotropy, but did preferentially increase surface diffusion rates on {310} regions.     

Fast lithium-ion transport in composites containing lithium-bromide dihydrate

Composites containing lithium-bromide dihydrates and a second phase, either the monohydrate or dispersed Al₂O₃ particles, exhibit an abrupt increase in the electrical conductivity at thedihydrate melting temperature T_m = 43°C. Although the conductivity at T >62 T_m is characteristic of a good liquid electrolyte -σ ≈ 0.1 mho cm^-1 at 130°C with an activation energy E_A = 13 kJ/mol and a Li⁺-ion transport number 0.9 ± 0.2, the composite pellet may be handled as a solid; it is brittle at 100°C. The possible significance of this finding for the design of high-power battery electrodes is indicated.     

Une détermination du coefficient d'autodiffusion de surface en présence d'une couche d'adsorption à l'aide de pointes àémission de champ (nickel sur tungsténe)

The tip blunting technique to measure the surface self-diffusion of clean metals (A. Piquet, Vu Thien Binh, H. Roux, R. Uzan and M. Drechsler) is extended to study the influence of an adsorption layer on diffusion. The system studied is nickel on tungsten. The increase of the apex radius is measured by means of FEM characteristics. In the temperature range used (1200–1500 K), the nickel monolayer (1.16 × 10¹⁵ atoms/cm²) is maintained by compensation of desorbed Ni atoms with a continual flux from an evaporation source. The adsorption life time between 1350 and 1500 K decreases from 850 to 16 s. The conservation of the degree of coverage leads to a method to determine the desorption activation energy of nickel (E_d = 4.56 eV/atom). The surface self-diffusion data of tungsten with a nickel monolayer are found to be D₀ = 3 × 10^?3cm/²s and Q_s = 1.9 eV/atom, compared to the clean tungsten data D₀ = 1 cm²/s and Q_s = 3.1 eV/atom. The Ni monolayer increases the surface self-diffusion coefficient by a factor 160 at 1200 K and 20 at 1500 K. The results are discussed with respect to nickel activated sintering of tungsten powders.     

Total width of the lowest T = 2 state in 24Mg

By analyzing thick-target excitation functions of the $\text{E}{}_{\mathrm{<mtext>p</mtext>}}\text{= 3906}\text{keV}{}^{23}\text{Na}\text{(}\text{p}\text{, γ)}$ resonance we have determined Γ_c.m ≦ 530⁺⁴⁰_?70 eV for the width of the lowest T = 2 state of ²⁴Mg. The beam energy resolution function was measured using a narrow ²⁷Al(p, γ) resonance at E_p = 3671 keV, for which we obtain Γ_c.m. = 180 ±50 eV.     

A statistical fMRI model for differential T2* contrast incorporating T1 and T2* of gray matter

Relaxation parameter estimation and brain activation detection are two main areas of study in magnetic resonance imaging (MRI) and functional magnetic resonance imaging (fMRI). Relaxation parameters can be used to distinguish voxels containing different types of tissue whereas activation determines voxels that are associated with neuronal activity. In fMRI, the standard practice has been to discard the first scans to avoid magnetic saturation effects. However, these first images have important information on the MR relaxivities for the type of tissue contained in voxels, which could provide pathological tissue discrimination. It is also well-known that the voxels located in gray matter (GM) contain neurons that are to be active while the subject is performing a task. As such, GM MR relaxivities can be incorporated into a statistical model in order to better detect brain activation. Moreover, although the MR magnetization physically depends on tissue and imaging parameters in a nonlinear fashion, a linear model is what is conventionally used in fMRI activation studies. In this study, we develop a statistical fMRI model for Differential T₂^? ConTrast Incorporating T₁ and T₂^? of GM, so-called DeTeCT-ING Model, that considers the physical magnetization equation to model MR magnetization; uses complex-valued time courses to estimate T₁ and T₂^? for each voxel; then incorporates gray matter MR relaxivities into the statistical model in order to better detect brain activation, all from a single pulse sequence by utilizing the first scans.     

Surface mass diffusion and step stiffness on an anisotropic surface; Mo(0 1 1)

Results of step fluctuation experiments for Mo(0 1 1), using low-energy electron microscopy, are re-examined using recently developed procedures that offer accurate coefficients of surface mass diffusion. By these means, surface diffusion D_s is documented at T/T_m ∼ 0.5, while the crossover to relaxation driven by bulk vacancy diffusion is inferred for T/T_m ∼ 0.6. Here, T_m is the melting temperature T_m = 2896 K. We obtain D_s = 4 × 10⁻⁴ exp(−1.13 eV/k_BT) cm²/s for the temperature interval 1080-1680 K. Possible indications of diffusion along step edges appear for T/T_m ∼ 0.4. The same measurements of step fluctuation amplitudes determine also the step stiffness, which by symmetry is anisotropic on Mo(0 1 1). It is shown that three independent procedures yield mutually consistent step stiffness anisotropies. These are (1) step fluctuation amplitudes; (2) step relaxation rate anisotropies; and (3) the observed anisotropies of islands in equilibrium on the Mo(0 1 1) surface. The magnitude of the step stiffness obtained from step edge relaxation is consistent with earlier measurements that determine diffusion from grain boundary grooving.     

Hall effect in n-type GaS

Hall effect measurements have been performed for the first time on n-type GaS single crystals, grown buy the Bridgam-Stockbarger method. Electrical properties are dominated by a donor centre at 0.52 eV, with a concentration of 2.3 × 10¹⁶cm^–3. The conduction band density-of-states effective mass has been estimated to be 1.3m_e.The low temperature conduction is compatible with a hopping process with an activation energy of 0.15 eV.     

Infrared spectroscopy of the intermediate-valence semiconductor YbB12

The dynamic conductivity and permittivity spectra of the intermediate-valence compound YbB₁₂ are measured in the frequency range (6–10⁴) cm^?1 (quantum energy 0.75 meV-1.24 eV) at temperatures of 5–300 K. Analysis of the spectral singularities associated with the response of free charge carriers has made it possible for the first time to determine the temperature dependences of their microscopic parameters, viz., concentration, effective mass, relaxation frequency and time, mobility, and plasma frequency. It is shown that the relaxation frequency decreases upon cooling from 300 K to the coherence temperature T ^* = 70 K for YbB₁₂, which is mainly associated with the phonon mechanism of scattering of charge carriers. For cooling below the coherence temperature T ^* = 70 K, the temperature dependence of the relaxation frequency for charge carriers of the Fermi-liquid type is found to be γ ～ γ₀ + T ², while their effective mass and relaxation time increase, respectively, to m ^*(20 K) = 34m ₀ (m ₀ is the free electron mass) and τ(20 K) = 4 × 10^?13 s, indicating the establishment of coherent scattering of carriers from localized magnetic moments of the f centers. At a temperature of T = 5 K, the conductivity spectrum contains an absorption line at a frequency of 22 cm^?1 (2.7 meV); the origin of this line can be associated with the exciton-polaron bound state. Since such a state was observed earlier in other intermediate-valence semiconductors (such as SmB₆, TmSe_1?x Te, and (Sm, Y)S), it is probably typical of this class of compounds.     

Resonant Raman scattering of CdCr2Se4

The scattering cross section of the Raman-active phonons at 156 cm^?1 (Eg) and 169 cm^?1 (F2g) in the ferromagnetic semiconductor CdCr₂Se₄ (T_c=130 K) has been measured as a function of incident photon energy between 1.55 and 2.81 eV, both in the ferromagnetic and paramagnetic phases. The resonance curve peaks sharply near 2 eV and shows a broadening for temperatures below the Curie point. The relative line intensities change significantly with photon energy. The results show that the concept of spin-dependent Raman scattering in the ferromagnetic spinels has to be revised in terms of exchange-splitting-induced resonant Raman scattering.     

Molecular binding states on clean and oxidized surfaces: SiO(g) + W(clean) and SiO(g) + W(oxidized)

The interactions between a molecular beam of SiO(g) and a clean and an oxidized tungsten surface were examined in the surface temperature range 600 to 1700 K by mass spectrometrically determined sticking probabilities, by flash desorption mass spectrometry (FDMS) and by Auger electron spectroscopy (AES). The sticking probability, S, of SiO has been determined as a function of coverage and of surface temperature for the clean and the oxidized tungsten surface. Over the temperature range studied and at zero coverage S = 1.0 and 0.88 for the clean and oxidized tungsten surfaces respectively. The results are consistent with both FDMS and AES. For coverage up to one monolayer there is one major adsorption state of SiO on the clean tungsten surface. FDMS shows that T_m = constant (T_m is the surface temperature at which the desorption rate is maximum) and that desorption from this state is described by a simple first order desorption process with activation energy, E_d = 85.3 kcal mole^?1 and pre-exponential factor, ν = 2.1 × 10¹⁴ sec^?1. AES shows that the 92 eV peak characteristic of silicon dominates. In contrast on the oxidized tungsten surface, T_m shifts to higher temperatures with increasing coverage. The data indicate a first order desorption process with a coverage dependent activation energy. At low coverage (θ ? 0.14) there is an adsorption state with E_d = 120 kcal mole^?1 and ν = 7.6 × 10¹⁹, while at θ = 1.0, E_d = 141 kcal mole^?1. This variation is interpreted as due to complex formation on the surface. AES shows that on oxidized tungsten, in contrast to clean tungsten, the dominant peaks occur at 64 and 78 eV, and these peaks are characteristic of higher oxidation states of silicon. Thus, it is concluded that SiO exists in different binding states on clean and oxidized tungsten surfaces.     

Une détermination du coefficient d'auto-diffusion de surface du molybdène

A recent study on the morphological evolution of a metal tip has shown that free evaporation must have a vital influence on the determination of the surface self-diffusion coefficient D_s in the high temperature region. We now present a method which enables the experimental determination of D_s: (1) in the presence of an evaporation, and (2) in a relatively great region of temperature. As an example, D_s of molybdenum has been measured. We obtain: (1) activation energy Q_s = 48.3 kcal/mole and diffusivity D_o = 0.3 cm²/sec for T < 0.6T_F (T_F melting temperature), and (2) Q_s = 76.7 kcal/mole and D_o = 690 cm²/sec for 0.65 T_F < T < 0.85 T_F; which indicate a change of the diffusion mechanism at about 0.65 T_F.