Understanding and predicting the dominant diffusion processes in Cr2O3 is essential to its optimization for anti-corrosion coatings, spintronics, and other applications. Despite significant theoretical effort in modeling defect mediated diffusion in Cr2O3 the correlation with experimentally measured diffusivities remains poor partly due to the insufficient accuracy of the theoretical approaches. Here an attempt to resolve these discrepancies is made through high accuracy density functional theory simulations coupled with grand canonical formalism of defect thermochemistry. In this approach, point defect formation energies were computed using hybrid exchange correlation functional. This level of theory proved to be essential for achieving the agreement with experimental self-diffusion coefficients. The analysis of the resulting self-diffusion coefficients indicate that chromium has higher mobility at low temperatures and high oxygen partial pressures, in particular at standard temperature and pressure conditions. At high vacuum, high temperature conditions, oxygen diffusion becomes dominant. At Cr/Cr2O3 interfaces O vacancies were found to be more mobile than Cr vacancies at all temperatures. Cr diffuses preferentially along the c-axis at low temperatures but switches to basal plane at higher temperatures. O diffusion is primarily bound to basal plane at all temperatures.
Diffusion couple technique is an efficient tool for the estimating the chemical diffusion coefficients. Typical experimental uncertainties of the composition profile measurements complicate a correct determination of the interdiffusion coefficients via the standard Boltzmann-Matano, Sauer-Freise or the den Broeder methods, especially for systems with a strong compositional dependence of the interdiffusion coefficient. A new approach for reliable fitting of the experimental profiles with an improved behavior at both ends of the diffusion couple is proposed and tested against the experimental da…
We report the prediction of temperature-dependent diffusion coefficients of interstitial hydrogen, deuterium, and tritium atoms in $α$-Ti using transition state theory. The microscopic parameters in the pre-factor and activation energy of the impurity diffusion coefficients are obtained from first-principles total energy and phonon calculations including the full coupling between the vibrational modes of the diffusing atom with the host lattice. The dual occupancy case of impurity atom in the hcp matrix are considered, and four diffusion paths are combined to obtain the final diffusion coeffic…
The LaAlO3/SrTiO3 (001) thin film materials system was studied using in situ, simultaneous x-ray diffuse scattering and specular reflectivity during pulsed laser deposition. Using this method, we are able to measure the time dependence of the characteristic surface length scale and the characteristic time for both in-plane and downhill diffusion. These data allow for the determination of the activation energy for various diffusion processes as a function of LaAlO3 thickness. Additionally, we show that the downhill diffusion rate of the first monolayer is distinctly different than subsequent la…
The Hanle-type spin precession method was carried out associated with non-local magnetoresistance measurement using a highly doped (5\times10^19) silicon channel. The spin diffusion length obtained by the Hanle-method is in good agreement with that by the gap dependence of non-local signals. We have evaluated the interface and bulk channel effects separately, and it was demonstrated that the major source of temperature dependence of non-local signals originates from the spin polarization reduction at interface between the tunnel barrier and silicon.
First-principles molecular dynamics simulations have been employed to analyze the proton diffusion in cubic BaZrO3 perovskite at 1300K, and a non-linear effect of an applied isometric strain of 2% on the lattice parameter has been observed. The structural and electronic properties of BaZrO3 are analyzed, based on Density Functional Theory calculations, and after an analysis of the electronic structure, we provide a possible explanation for an enhanced ionic conductivity, that can be caused by the formation of a preferential path for proton diffusion under compressive strain conditions.
We conduct an experimental investigation of temperature dependence of spin diffusion length in highly-doped n-type silicon by using a non-local 3-terminal method. Whereas an effect of spin drift is not ignorable to bias- and temperature-dependence of spin signals in non-metallic systems except for the case of a non-local 4-terminal method, it is not fully conclusive how the spin drift affects spin transport properties in highly-doped Si in a non-local 3-terminal method that is often used in Si spintronics. Here, we report on temperature dependence of spin diffusion length in the Si, and it is …
We study the influence of the boundary conditions at the solid liquid interface on diffusion in a confined fluid. Using an hydrodynamic approach, we compute numerical estimates for the diffusion of a particle confined between two planes. Partial slip is shown to significantly influence the diffusion coefficient near a wall. Analytical expressions are derived in the low and high confinement limits, and are in good agreement with numerical results. These calculations indicate that diffusion of tagged particles could be used as a sensitive probe of the solid-liquid boundary conditions.
MD simulations reveal that many aspects of SWNT nucleation and growth from solid and liquid metal particles are similar. In both cases graphitic islands lift off the cluster surface to form caps that grow into SWNTs. However, in contrast to liquid particles, where C atoms primarily diffuse into the bulk of the cluster before adding to the growing SWNT, incorporation of C into SWNTs on solid particles occurs predominantly via surface diffusion.
The temperature-dependent diffusion coefficients of interstitial helium atom in $α$-Ti are predicted using the transition state theory. The microscopic parameters in the pre-factor and activation energy of the impurity diffusion coefficients are obtained from first-principles total energy and phonon calculations including the full coupling between the vibrational modes of the diffusing atom and the host lattice. The climbing image nudged elastic band (CINEB) method is used to search for the minimum energy pathways and associated saddle point structures. It is demonstrated that the diffusion co…
Using density-functional theory with the local-density approximation and the generalized gradient approximation we compute the energy barriers for surface diffusion for Ag on Pt(111), Ag on one monolayer of Ag on Pt(111), and Ag on Ag(111). The diffusion barrier for Ag on Ag(111) is found to increase linearly with increasing lattice constant. We also discuss the reconstruction that has been found experimentally when two Ag layers are deposited on Pt(111). Our calculations explain why this strain driven reconstruction occurs only after two Ag layers have been deposited.
The incorporation and diffusion of helium (He) with and without intrinsic vacancy defects in cubic ZrO$_{2}$ are investigated through first-principles total-energy calculations, in which the projector-augmented-wave (PAW) method with the generalized gradient approximation (GGA) is used. The calculated formation energies of intrinsic point defects indicate that cubic ZrO$_{2}$ has a tolerant resistance to radiation damage. The incorporation energy of He impurity shows that it is preferable to occupy the Zr vacancy at first, whereas the solution energy suggests that He would be accommodated in t…
The problem of estimation of the tracer diffusion coefficients is solved by utilizing a novel tracer-interdiffusion couple technique even in the absence suitable radioisotope of one of the components and absence of reliable thermodynamic parameters. This is demonstrated by generating reliable and reproducible mobility data in the alloys of the Fe-Ga system with a strong composition dependence of the diffusion coefficients. Tracer- (59Fe) and inter-diffusion are simultaneously measured in three couples Fe/Fe-16Ga, Fe/Fe-24Ga and Fe-16Ga/Fe-24Ga at 1143 K. The results obtained for the couples wi…
We report first-principles analysis on the bias dependence of spin-transfer torque (STT) in Fe/MgO/Fe magnetic tunnel junctions. The in-plane STT changes from linear to nonlinear dependence as the bias voltage is increased from zero. The angle dependence of STT is symmetric at low bias but asymmetric at high bias. The nonlinear behavior is marked by a threshold point in the STT versus bias curve. The high-bias nonlinear STT is found to be controlled by a resonant transmission channel in the anti-parallel configuration of the magnetic moments. Disorder scattering due to oxygen vacancies in MgO …
The effects of Li doping in MgH$_2$ on H-diffusion process are investigated, using first-principles calculations. We have identified two key effects: (1) The concentration of H vacancy in the $+1$ charge state (V$_H^{+1}$) can increase by several orders of magnitude upon Li doping, which significantly increases the vacancy mediated H diffusion rate. It is caused by the preferred charge states of substitutional Li in the $-1$ state (Li$_{Mg}^{-1}$) and of interstitial Li in the $+1$ state (Li$_i^{+1}$), which indirectly reduce the formation energy of V$_H^{+1}$ by up to 0.39 eV depending on the…
We have studied diffusion pathways of a silyl radical adsorbed on the hydrogenated Si (100)-(2x1) surface by density-functional theory. The process is of interest for the growth of crystalline silicon by plasma-enhanced chemical vapor deposition. Preliminary searches for migration mechanisms have been performed using metadynamics simulations. Local minima and transition states have been further refined by using the nudged-elastic-band method. Barriers for diffusion from plausible adsorption sites as low as 0.2 eV have been found, but trap states have also been spotted, leading to a more stable…
The light elemental solutes B, C, N, and O can penetrate the surface of Mg alloys and diffuse during heat treatment or high temperature application, forming undesirable compounds. We investigate the diffusion of these solutes by determining their stable interstitial sites and the inter-penetrating network formed by these sites. We use density functional theory (DFT) to calculate the site energies, migration barriers, and attempt frequencies for these networks to inform our analytical model for bulk diffusion. Due to the nature of the networks, O diffuses isotropically, while B, C, and N diffus…
Spatiotemporal dynamics of electron-hole pairs locally excited in a silicon-on-insulator structure by indirect interband absorption are studied by measuring differential transmission caused by free-carrier absorption of a probe pulse tuned below the bandgap, with 200-fs temporal and 3-micrometer spatial resolution. From sample temperatures of 250 K to 400 K, the ambipolar diffusivity decreases, and is similar to reported values of bulk silicon. Cooling the sample from 250 K to 90 K, a decrease of ambipolar diffusivity is observed, indicating important influences of defects and residual stress …
First-principles calculations are used to calculate the strain dependencies of the binding and diffusion-activation energies for Ge adatoms on both Si(001) and Ge(001) surfaces. Our calculations reveal that the binding and activation energies on a strained Ge(001) surface increase and decrease, respectively, by 0.21 eV and 0.12 eV per percent compressive strain. For a growth temperature of 600 degrees C, these strain-dependencies give rise to a 16-fold increase in adatom density and a 5-fold decrease in adatom diffusivity in the region of compressive strain surrounding a Ge island with a chara…
Spin transport in magnetic tunnel junctions in the presence of spin diffusion is considered theoretically. Combining ballistic tunneling across the barrier and diffusive transport in the electrodes, we solve the spin dynamics equation in the metallic layers. We show that spin diffusion mixes the transverse spin current components and dramatically modifies the bias dependence of the effective spin transfer torque. This leads to a significant linear bias dependence of the out-of-plane torque, as well as a non-conventional thickness dependence of both spin torque components.
A variation principle for mass transport in solids is derived that recasts transport coefficients as minima of local thermodynamic average quantities. The result is independent of diffusion mechanism, and applies to amorphous and crystalline systems. This unifies different computational approaches for diffusion, and provides a framework for the creation of new approximation methods with error estimation. It gives a different physical interpretation of the Green function. Finally, the variational principle quantifies the accuracy of competing approaches for a nontrivial diffusion problem.
The reported diffusion constants for hydrogen in silicon vary over six orders of magnitude. This spread in measured values is caused by the different concentrations of defects in the silicon that has been studied. Hydrogen diffusion is slowed down as it interacts with impurities. By changing the material properties such as the crystallinity, doping type and impurity concentrations, the diffusivity of hydrogen can be changed by several orders of magnitude. In this study the influence of the hydrogen concentration on the temperature dependence of the diffusion in high energy proton implanted sil…
Using a formulation of first-principles scattering theory that includes disorder and spin-orbit coupling on an equal footing, we calculate the resistivity $ρ$, spin flip diffusion length $l_{sf}$ and the Gilbert damping parameter $α$ for Ni$_{1-x}$Fe$_x$ substitutional alloys as a function of $x$. For the technologically important Ni$_{80}$Fe$_{20}$ alloy, permalloy, we calculate values of $ρ= 3.5 \pm 0.15$ $μ$Ohm-cm, $l_{sf}=5.5 \pm 0.3$ nm, and $α= 0.0046 \pm 0.0001$ compared to experimental low-temperature values in the range $4.2-4.8$ $μ$Ohm-cm for $ρ$, $5.0-6.0$ nm for $l_{sf}$, and $0.00…
The swelling dynamics of polymer gels are characterized by the (collective) diffusion coefficient $D$ of the polymer network. Here, we measure the temperature dependence of $D$ of polymer gels with controlled homogeneous network structures using dynamic light scattering. An evaluation of the diffusion coefficient at the gelation point $D_{\mathrm{gel}}$ and the increase therein as the gelation proceeds $ΔD\equiv D-D_{\mathrm{gel}}$ indicates that $ΔD$ is a linear function of the absolute temperature with a significantly large negative constant term. This feature is formally identical to the re…
Crystallization kinetics has features that are universal and independent of the type of crystallized system. The possibility of using scaling relations to describe the temperature dependences of the surface self-diffusion coefficient $D_s$, which is one of the key characteristics of crystallization kinetics, has been demonstrated in application to various crystallized molecular glasses. It has been shown that the surface self-diffusion coefficient $D_s$ as a function of the dimensionless temperature is reproduced by a power law and is universally scaled for all considered systems. The analysis…
