Implications of the DFT plus U method on polaron properties in energy materials

To model polaronic behavior in strongly correlated transition-metal oxideswith ab initio methods, one typically requires a level of theory beyond that of local density or general gradient density functional theory (DFT) approximations to account for the strongly correlated d-shell interactions of transition-metal oxides. In the present work, we utilize density functional theory with additional on-site Hubbard corrections (DFT+ U) to calculate polaronic properties in two lithium ion battery cathode materials, Li x FePO4 and Li x Mn2O4, and two photocatalytic materials, TiO2 and Fe2O3. We investigate the effects of the + U on-site projection on polaronic properties. Through systematic comparison with hybrid functional calculations, it is shown that + U projection in these model materials can impact upon the band gap, polaronic hopping barrier, and polaronic eigenstate offset from the band edges in a nontrivial manner. These properties are shown to have varying degrees of coupling and dependence on the + U projection in each example material studied, which has important implications for arriving at systematic material predictions of polaronic properties in transition-metal oxides.

Nonempirical hybrid functionals for advanced electronic-structure calculations

Thomas Bischoff

Electronic-structure calculations based on hybrid functionals have emerged as a standard technique used in physics, chemistry, and material science. Despite this success, hybrid functionals have the drawback of containing undetermined parameters. To overcome this deficiency, two different nonempirical determination schemes are being investigated at present, namely dielectric-dependent hybrid (DDH) functionals and hybrid functionals that satisfy Koopmans' condition. This thesis is dedicated to the examination and further development of these approaches. In particular, we show that a precise description of band gaps in condensed-matter systems can be achieved with these functionals. Moreover, we demonstrate that their accuracy is comparable to state-of-the-art

GW

methods while requiring substantially lower computational cost. First, we focus on the development of hybrid functionals satisfying Koopmans' condition. We show that the construction of those functionals can be optimized through suitably defined potential probes. By monitoring the delocalized screening charge, we achieve a measure of the degree of hybridization with the band states, which can be used to improve the band-gap estimate. We show that the application of this methodology to common semiconducting and insulating materials yields band gaps differing by less than 0.2 eV from experiment. These conceptual developments are an important step towards establishing hybrid functionals satisfying Koopmans' condition as a robust approach for band-gap predictions. Second, we examine DDH functionals and hybrid functionals satisfying Koopmans' condition for band gaps of more sophisticated materials. In particular, we focus on inorganic metal-halide perovskites which have recently drawn great scientific attention. For this class of materials, we show that both nonempirical hybrid-functional schemes yield band gaps of comparable accuracy (

\sim

0.2 eV) with respect to

GW

reference calculations. Furthermore, we discuss the suitability of nonempirical hybrid-functional schemes for the application to the screening of large sets of perovskite materials. Third, we investigate the fundamental band gap of liquid water and hexagonal ice. These materials are particularly challenging since experimental studies have not reached a consensus on the band gap yet. Therefore, we first deduce robust benchmarks on the basis of a critical review of various experimental studies in the literature. Then, we compute the band gap through state-of-the-art

GW

methods as well as nonempirical hybrid functionals. We show that theoretical calculations and experimental references are in good agreement with each other and we discuss critical aspects which are essential to ensure a consistent description of the band gap. Finally, we investigate band-edge levels as obtained with hybrid-functional calculations. The CaF

_2

/Si(111) interface serves thereby as an ideal test case to examine the accuracy of different theoretical schemes. The comparison with experiment reveals that global hybrid functionals and self-consistent

GW

methods provide the most accurate description of the interfacial band alignment.

EPFL2021

First-principles study of defects at the SiC/SiO2 interface through hybrid functionals

Fabien Devynck

The requirements of present high-performance power electronic systems are exceeding the power density, efficiency, and reliability of silicon-based devices. Silicon carbide (SiC) is a candidate of choice for high-temperature, high-speed, high-frequency, and high-power applications: it has a wide band gap, high thermal conductivity, high saturated electron drift velocity, and high breakdown electric field. SiC is also hard, chemically stable, and resistant to radiation damage. Despite these desirable electronic properties, SiC-based devices are still facing many performance challenges due to the high density of defect states at the SiC/SiO2 interface. This thesis is dedicated to the first-principles study of defects at the SiC/SiO2 interface through hybrid functionals. We first generate a model structure providing a realistic description of the majority bonding arrangements at the 4H(0001)-SiC/SiO2 interface. The description of the electronic structure of the model through hybrid functionals leads to band offsets in excellent agreement with their experimental counterparts. We then study several semiconductor and oxide defects using spin-polarized hybrid density functionals and identify candidate defects responsible for the high density of interface defects measured in the 4H-SiC band gap. Finally, the possibility of growing epitaxial silicate adlayers on SiC is investigated as an alternative approach to greatly reduce the high density of defect states at the SiC/SiO2 interface.

EPFL2008

Structural and electronic properties of an abrupt 4H-SiC(0001)/SiO2 interface model: Classical molecular dynamics simulations and density functional calculations

Peter Broqvist, Fabien Devynck, Alfredo Pasquarello

Using a density functional approach, we study structural and electronic properties of the 4H(0001)-SiC/SiO2 interface. Through the sequential use of classical and ab initio simulation methods, we generate an abrupt model structure which describes the transition between crystalline SiC and amorphous SiO2 without showing any coordination defect. The first step in our generation procedure consists in identifying suitable interfacial bonding patterns which account for the bond density reduction across the interface. In the second step, the connection to amorphous SiO2 is achieved through classical molecular dynamics. The atomic positions are then relaxed within a generalized gradient approximation of density functional theory. The final model structure shows good structural parameters and an oxide density typical of amorphous SiO2. We investigate the electronic structure of the generated model interface through the local density of states obtained with hybrid density functionals. In our atomically abrupt interface model, the full oxide band gap is recovered at a distance of similar to 5 A from the interface. This extent is in good agreement with estimates derived from internal photoemission measurements and provides support for the abrupt nature of the interface. We obtained band offsets through two different procedures: by evaluating the local density of states and by aligning the band extrema through the local electrostatic potential. Band offsets calculated with various functionals are compared to experimental values. The best agreement is achieved for a hybrid functional in which a screened Coulomb potential is used in the Hartree-Fock exchange term. For this case, the calculated band offsets underestimate the experimental values by similar to 25%, but agree with experiment within a few percent when expressed with respect to the oxide band gap.

2007