Brown, Nicholas Taylor

DOE OSTI2017

On the mobility of carriers at semi-coherent oxide heterointerfaces

In the quest to develop new materials with enhanced ionic conductivity for battery and fuel cell applications, nano-structured oxides have attracted attention. Experimental reports indicate that oxide heterointerfaces can lead to enhanced ionic conductivity, but these same reports cannot elucidate the origin of this enhancement, often vaguely referring to pipe diffusion at misfit dislocations as a potential explanation. However, this highlights the need to understand the role of misfit dislocation structure at semi-coherent oxide heterointerfaces in modifying carrier mobilities. Here, we use atomistic and kinetic Monte Carlo (KMC) simulations to develop a model of oxygen vacancy migration at SrTiO 3 /MgO interfaces, chosen because the misfit dislocation structure can be modified by changing the termination chemistry. We use atomistic simulations to determine the energetics of oxygen vacancies at both SrO and TiO 2 terminated interfaces, which are then used as the basis of the KMC simulations. While this model is approximate (as revealed by select nudged elastic band calculations), it highlights the role of the misfit dislocation structure in modifying the oxygen vacancy dynamics. We find that oxygen vacancy mobility is significantly reduced at either interface, with slight differences at each interface due to the differing misfit dislocation structure. Here, we conclude that if such semi-coherent oxide heterointerfaces induce enhanced ionic conductivity, it is not a consequence of higher carrier mobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Modeling material interfaces with hybrid adhesion method

A molecular dynamics simulation approach is presented to approximate layered material structures using discrete interatomic potentials through classical mechanics and the underlying principles of quantum mechanics. This method isolates the energetic contributions of the system into two pure material layers and an interfacial region used to simulate the adhesive properties of the diffused interface. The strength relationship of the adhesion contribution is calculated through small-scale separation calculations and applied to the molecular surfaces through an inter-layer bond criterion. By segregating the contributions into three regions and accounting for the interfacial excess energies through the adhesive surface bonds, it is possible to model each material with an independent potential while maintaining an acceptable level of accuracy in the calculation of mechanical properties. This method is intended for the atomistic study of the delamination mechanics, typically observed in thin-film applications. Therefore, the work presented in this paper focuses on mechanical tensile behaviors, with observations in the elastic modulus and the delamination failure mode. To introduce the hybrid adhesion method, we apply the approach to an ideal bulk copper sample, where an interface is created by disassociating the force potential in the middle of the structure. Various mechanical behaviors are compared to a standard EAM control model to demonstrate the adequacy of this approach in a simple setting. In addition, we demonstrate the robustness of this approach by applying it on (1) a Cu-Cu 2 O interface with interactions between two atom types, and (2) an Al-Cu interface with two dissimilar FCC lattices. These additional examples are verified against EAM and COMB control models to demonstrate the accurate simulation of failure through delamination, and the formation and propagation of dislocations under loads. Finally, the results conclude that by modeling the energy contributions of an interface using hybrid adhesion bonds, we can provide an accurate approximation method for studies of large-scale mechanical properties, as well as the representation of various delamination phenomena at the atomic scale.

36 MATERIALS SCIENCE↗