Effect of manganese doping on the size effect of lead zirconate titanate thin films and the extrinsic nature of dead layers

We have investigated the size effect in lead zirconate titanate (PZT) thin films with a range of manganese (Mn) doping concentrations. We found that the size effect in the conventional Pt/PZT/Pt thin-film capacitors could be systematically reduced and almost completely eliminated by increasing Mn doping concentration. The interfacial layer at the electrode-film interface appears to disappear almost entirely for the PZT films with 2% Mn doping levels, confirmed by the fits using the conventional in-series capacitor model. Our work indicates that the size effect in ferroelectrics is extrinsic in nature, supporting the work by Saad et al. Other implications of our results have also been discussed. By comparing a variety of experimental studies in the literature we propose a scenario that the dead layer between PZT (or barium strontium titanate, BST) and metal electrodes such as Pt and Au might have a defective pyrochlore/fluorite structure (possibly with a small portion of ferroelectric perovskite phase).Comment: 21 pages, 6 figure

Chebyshev polynomial filtered subspace iteration in the Discontinuous Galerkin method for large-scale electronic structure calculations

The Discontinuous Galerkin (DG) electronic structure method employs an adaptive local basis (ALB) set to solve the Kohn-Sham equations of density functional theory (DFT) in a discontinuous Galerkin framework. The adaptive local basis is generated on-the-fly to capture the local material physics, and can systematically attain chemical accuracy with only a few tens of degrees of freedom per atom. A central issue for large-scale calculations, however, is the computation of the electron density (and subsequently, ground state properties) from the discretized Hamiltonian in an efficient and scalable manner. We show in this work how Chebyshev polynomial filtered subspace iteration (CheFSI) can be used to address this issue and push the envelope in large-scale materials simulations in a discontinuous Galerkin framework. We describe how the subspace filtering steps can be performed in an efficient and scalable manner using a two-dimensional parallelization scheme, thanks to the orthogonality of the DG basis set and block-sparse structure of the DG Hamiltonian matrix. The on-the-fly nature of the ALBs requires additional care in carrying out the subspace iterations. We demonstrate the parallel scalability of the DG-CheFSI approach in calculations of large-scale two-dimensional graphene sheets and bulk three-dimensional lithium-ion electrolyte systems. Employing 55,296 computational cores, the time per self-consistent field iteration for a sample of the bulk 3D electrolyte containing 8,586 atoms is 90 seconds, and the time for a graphene sheet containing 11,520 atoms is 75 seconds.Comment: Submitted to The Journal of Chemical Physic