Band alignment at metal/ferroelectric interfaces: insights and artifacts from first principles

Abstract

Based on recent advances in first-principles theory, we develop a general model of the band offset at metal/ferroelectric interfaces. We show that, depending on the polarization of the film, a pathological regime might occur where the metallic carriers populate the energy bands of the insulator, making it metallic. As the most common approximations of density functional theory are affected by a systematic underestimation of the fundamental band gap of insulators, this scenario is likely to be an artifact of the simulation. We provide a number of rigorous criteria, together with extensive practical examples, to systematically identify this problematic situation in the calculated electronic and structural properties of ferroelectric systems. We discuss our findings in the context of earlier literature studies, where the issues described in this work have often been overlooked. We also discuss formal analogies to the physics of polarity compensation at LaAlO3/SrTiO3 interfaces, and suggest promising avenues for future research.

29 pages, 23 figures

References in corpus (28)

• The SIESTA method for ab initio order-N materials simulation
• Efficient index handling of multidimensional periodic boundary conditions
• Maximally-localized generalized Wannier functions for composite energy bands
• Physics of thin-film ferroelectric oxides
• Giant Electroresistance in Ferroelectric Tunnel Junctions
• Towards ferroelectrically-controlled magnetism: Magnetoelectric effect in Fe/BaTiO3 multilayers
• The physics of dynamical atomic charges: the case of ABO3 compounds
• A First-Principles Approach to Insulators in Finite Electric Fields
• Enhancement of ferroelectricity at metal/oxide interfaces
• Hybrid exchange-correlation functional for accurate prediction of the electronic and structural properties of ferroelectric oxides
• Theory of polarization enhancement in epitaxial BaTiO${}_3$/SrTiO${}_3$ superlattices
• Carrier-mediated magnetoelectricity in complex oxide heterostructures
• Ferroelectricity in ultra-thin perovskite films
• Interface-Controlled Ferroelectricity at the Nanoscale
• Electric displacement as the fundamental variable in electronic-structure calculations
• Towards two-dimensional metallic behavior at LaAlO3/SrTiO3 interfaces
• Dynamics of Berry-phase polarization in time-dependent electric fields
• First-principles modeling of electrostatically doped perovskite systems
• First-principles calculation of the band offset at BaO/BaTiO${}_3$ and SrO/SrTiO${}_3$ interfaces
• Interface effects at a half-metal/ferroelectric junction
• Nanoscale Smoothing and the Analysis of Interfacial Charge and Dipolar Densities
• Berry-phase theory of polar discontinuities at oxide-oxide interfaces
• Ferroelectric Dead Layer Driven by a Polar Interface
• First-principles modeling of ferroelectric capacitors via constrained-D calculations
• Ab-initio theory of metal-insulator interfaces in a finite electric field
• Wannier-based definition of layer polarizations in perovskite superlattices
• Evolution of the band alignment at polar oxide interfaces
• Theoretical investigation of polarization-compensated II-IV/I-V perovskite superlattices

Cited by in corpus (36)

• Structure and properties of functional oxide thin films: Insights from electronic-structure calculations
• The Magnetoelectric Effect in Transition Metal Oxides: Insights and the Rational Design of New Materials from First Principles
• Electrostatic stability of insulating surfaces: Theory and applications
• Effect of a built-in electric field in asymmetric ferroelectric tunnel junctions
• Oxygen vacancies nucleate charged domain walls in ferroelectrics
• First-Principles Theory for Schottky Barrier Physics
• Full field electron spectromicroscopy applied to ferroelectric materials
• Coexistance of giant tunneling electroresistance and magnetoresistance in an all-oxide magnetic tunnel junction
• Interface Electronic Structure in a Metal/Ferroelectric Heterostructure under Applied Bias
• Ferroelectric control of magnetization in La_{1-x}Sr_xMnO3 manganites: A first-principle study
• Electrochemical ferroelectric switching: The origin of polarization reversal in ultrathin films
• Layer and spontaneous polarizations in perovskite oxides and their interplay in multiferroic bismuth ferrite
• Two-dimensional electron gas at the PbTiO${}_3$/SrTiO${}_3$ interface: an ab initio study
• Theory of polar domains in moiré heterostructures
• On the key role of oxygen vacancies electromigration in the memristive response of ferroelectric devices
• First-principles study of two-dimensional electron and hole gases at the head-to-head and tail-to-tail 180${}^{\circ }$ domain walls in PbTiO${}_3$ ferroelectric thin films
• First principles study of band line up at defective metal-oxide interface: oxygen point defects at Al/SiO_2 interface
• Theory of polarization textures in crystal supercells
• Coexistence of polar displacements and conduction in doped ferroelectrics: an ab initio comparative study
• First-Principles Modeling of Pt/LaAlO3/SrTiO3 Capacitors Under an External Bias Potential
• Flexoelectric radial polarization of single-walled nanotubes from first-principles
• Unveiling multiferroic proximity effect in graphene
• Ferroelectricity driven magnetism at domain walls in LaAlO${}_3$/PbTiO${}_3$ superlattices
• Photovoltaic response around a unique180{\textdegree} ferroelectric domain wall in single crystalline BiFeO3
• Novel magneto-electric multiferroics from first-principles
• Interface control of ferroelectricity in LaNiO3-BaTiO3 superlattices
• Ab initio study of the TiO${}_2$ Rutile(110)/Fe interface
• Octahedral Rotation Induced, Antiferroelectric-like Double Hysteresis in Strained Perovskites
• First-principles study of metal-induced gap states in metal/oxide interfaces and their relation with the complex band structure
• Electrochemical stability and light-harvesting ability of silicon photoelectrodes in aqueous environments
• Study of electronic and magnetic properties and related x-ray absorption spectroscopy of ultrathin Co films on BaTiO${}_3$
• Pressure-induced metal-insulator transition in oxygen-deficient LiNbO${}_3$-type ferroelectrics
• Ferroelectric Control of Metal-Insulator Transition
• Charge distribution at metal-multilayered semiconductor interfaces
• Interfacial phenomena in nanocapacitors with multifunctional oxides
• Electrostatic properties and current transport of two-dimensional Schottky barrier diode