First-principles Many-body Perturbation Theory Research Articles

Excitons in metal-halide perovskites from first-principles many-body perturbation theory

Metal-halide perovskites are a structurally, chemically, and electronically diverse class of semiconductors with applications ranging from photovoltaics to radiation detectors and sensors. Understanding neutral electron–hole excitations (excitons) is key for predicting and improving the efficiency of energy-conversion processes in these materials. First-principles calculations have played an important role in this context, allowing for a detailed insight into the formation of excitons in many different types of perovskites. Such calculations have demonstrated that excitons in some perovskites significantly deviate from canonical models due to the chemical and structural heterogeneity of these materials. In this Perspective, I provide an overview of calculations of excitons in metal-halide perovskites using Green’s function-based many-body perturbation theory in the GW + Bethe–Salpeter equation approach, the prevalent method for calculating excitons in extended solids. This approach readily considers anisotropic electronic structures and dielectric screening present in many perovskites and important effects, such as spin–orbit coupling. I will show that despite this progress, the complex and diverse electronic structure of these materials and its intricate coupling to pronounced and anharmonic structural dynamics pose challenges that are currently not fully addressed within the GW + Bethe–Salpeter equation approach. I hope that this Perspective serves as an inspiration for further exploring the rich landscape of excitons in metal-halide perovskites and other complex semiconductors and for method development addressing unresolved challenges in the field.

Broken Symmetry Optical Transitions in (6,5) Single-Walled Carbon Nanotubes Containing sp3 Defects Revealed by First-Principles Theory.

We present a first-principles many-body perturbation theory study of nitrophenyl-doped (6,5) single-walled nanotubes (SWCNTs) to understand how sp3 doping impacts the excitonic properties. sp3-doped SWCNTs are promising as a class of optoelectronic materials with bright tunable photoluminescence, long spin coherence, and single-photon emission (SPE), motivating the study of spin excitations. We predict that the dopant results in a single unpaired spin localized around the defect site, which induces multiple low-energy excitonic peaks. By comparing optical absorption and photoluminescence from experiment and theory, we identify the transitions responsible for the red-shifted, defect-induced E11* peak, which has demonstrated SPE for some dopants; the presence of this state is due to both the symmetry-breaking associated with the defect and the presence of the defect-induced in-gap state. Furthermore, we find an asymmetry between the contribution of the two spin channels, suggesting that this system has potential for spin-selective optical transitions.

Tunable Interlayer Delocalization of Excitons in Layered Organic-Inorganic Halide Perovskites.

Layered organic-inorganic halide perovskites exhibit remarkable structural and chemical diversity and hold great promise for optoelectronic devices. In these materials, excitons are thought to be strongly confined within the inorganic metal halide layers with interlayer coupling generally suppressed by the organic cations. Here, we present an in-depth study of the energy and spatial distribution of the lowest-energy excitons in layered organic-inorganic halide perovskites from first-principles many-body perturbation theory, within the GW approximation and the Bethe-Salpeter equation. We find that the quasiparticle band structures, linear absorption spectra, and exciton binding energies depend strongly on the distance and the alignment of adjacent metal halide perovskite layers. Furthermore, we show that exciton delocalization can be modulated by tuning the interlayer distance and alignment, both parameters determined by the chemical composition and size of the organic cations. Our calculations establish the general intuition needed to engineer excitonic properties in novel halide perovskite nanostructures.

Effect of environmental screening and strain on optoelectronic properties of two-dimensional quantum defects

Point defects in hexagonal boron nitride (hBN) are promising candidates as single-photon emitters (SPEs) in nanophotonics and quantum information applications. The precise control of SPEs requires in-depth understanding of their optoelectronic properties. However, how the surrounding environment of host materials, including the number of layers, substrates, and strain, influences SPEs has not been fully understood. In this work, we study the dielectric screening effect due to the number of layers and substrates, and the strain effect on the optical properties of carbon dimer and nitrogen vacancy defects in hBN from first-principles many-body perturbation theory. We report that environmental screening causes a lowering of the quasiparticle gap and exciton binding energy, leading to nearly constant optical excitation energy and exciton radiative lifetime. We explain the results with an analytical model starting from the Bethe–Salpeter equation Hamiltonian with Wannier basis. We also show that optical properties of quantum defects are largely tunable by strain with highly anisotropic response, in good agreement with experimental measurements. Our work clarifies the effect of environmental screening and strain on optoelectronic properties of quantum defects in two-dimensional insulators, facilitating future applications of SPEs and spin qubits in low-dimensional systems.

Comparative Study of Covalent and van der Waals CdS Quantum Dot Assemblies from Many-Body Perturbation Theory.

Quantum dot (QD) assemblies are nanostructured networks made from aggregates of QDs and feature improved charge and energy transfer efficiencies compared to discrete QDs. Using first-principles many-body perturbation theory, we systematically compare the electronic and optical properties of two types of CdS QD assemblies that have been experimentally investigated: (i) QD gels, where individual QDs are covalently connected via di- or polysulfide bonds, and (ii) QD nanocrystals, where individual QDs are bound via van der Waals interactions. Our work illustrates how the electronic and optical properties evolve when discrete QDs are assembled into 1D, 2D, and 3D gels and nanocrystals, as well as how the one-body and many-body interactions in these systems impact the trends as the dimensionality of the assembly increases. Furthermore, our work reveals the crucial role of the di- or polysulfide covalent bonds in the localization of the excitons, which highlights the difference between QD gels and QD nanocrystals.

Optical and magneto-optical properties of ferromagnetic monolayer CrBr3 : A first-principles GW and GW plus Bethe-Salpeter equation study

The discovery of atomically thin two-dimensional (2D) magnetic semiconductors has triggered enormous research interest recently. In this work, we use first-principles many-body perturbation theory to study a prototypical 2D ferromagnetic semiconductor, monolayer chromium tribromide (CrBr$_3$). With broken time-reversal symmetry, spin-orbit coupling, and excitonic effects included through the full-spinor $GW$ and $GW$ plus Bethe-Salpeter equation ($GW$-BSE) methods, we compute the frequency-dependent layer polarizability tensor and dielectric function tensor that govern the optical and magneto-optical properties. In addition, we provide a detailed theoretical formalism for simulating magnetic circular dichroism, magneto-optical Kerr effect, and Faraday effect, demonstrating the approach with monolayer CrBr$_3$. Due to reduced dielectric screening in 2D and the localized nature of the Cr $d$ orbitals, we find strong self-energy effects on the quasiparticle band structure of monolayer CrBr$_3$ that give a 3.8 eV indirect band gap. Also, excitonic effects dominate the low-energy optical and magneto-optical responses in monolayer CrBr$_3$ where a large exciton binding energy of 2.3 eV is found for the lowest bright exciton state with excitation energy at 1.5 eV. We further find that the magneto-optical signals demonstrate strong dependence on the excitation frequency and substrate refractive index. Our theoretical framework for modeling optical and magneto-optical effects could serve as a powerful theoretical tool for future study of optoelectronic and spintronics devices consisting of van der Waals 2D magnets.

Substrate effect on excitonic shift and radiative lifetime of two-dimensional materials

Substrates have strong effects on optoelectronic properties of two-dimensional (2D) materials, which have emerged as promising platforms for exotic physical phenomena and outstanding applications. To reliably interpret experimental results and predict such effects at 2D interfaces, theoretical methods accurately describing electron correlation and electron-hole interaction such as first-principles many-body perturbation theory are necessary. In our previous work (2020 Phys. Rev. B 102 205113), we developed the reciprocal-space linear interpolation method that can take into account the effects of substrate screening for arbitrarily lattice-mismatched interfaces at the GW level of approximation. In this work, we apply this method to examine the substrate effect on excitonic excitation and recombination of 2D materials by solving the Bethe–Salpeter equation. We predict the nonrigid shift of 1s and 2s excitonic peaks due to substrate screening, in excellent agreements with experiments. We then reveal its underlying physical mechanism through 2D hydrogen model and the linear relation between quasiparticle gaps and exciton binding energies when varying the substrate screening. At the end, we calculate the exciton radiative lifetime of monolayer hexagonal boron nitride with various substrates at zero and room temperature, as well as the one of WS2 where we obtain good agreement with experimental lifetime. Our work answers important questions of substrate effects on excitonic properties of 2D interfaces.

Evidence of ideal excitonic insulator in bulk MoS2 under pressure

Spontaneous condensation of excitons is a long-sought phenomenon analogous to the condensation of Cooper pairs in a superconductor. It is expected to occur in a semiconductor at thermodynamic equilibrium if the binding energy of the excitons-electron (e) and hole (h) pairs interacting by Coulomb force-overcomes the band gap, giving rise to a new phase: the "excitonic insulator" (EI). Transition metal dichalcogenides are excellent candidates for the EI realization because of reduced Coulomb screening, and indeed a structural phase transition was observed in few-layer systems. However, previous work could not disentangle to which extent the origin of the transition was in the formation of bound excitons or in the softening of a phonon. Here we focus on bulk [Formula: see text] and demonstrate theoretically that at high pressure it is prone to the condensation of genuine excitons of finite momentum, whereas the phonon dispersion remains regular. Starting from first-principles many-body perturbation theory, we also predict that the self-consistent electronic charge density of the EI sustains an out-of-plane permanent electric dipole moment with an antiferroelectric texture in the layer plane: At the onset of the EI phase, those optical phonons that share the exciton momentum provide a unique Raman fingerprint for the EI formation. Finally, we identify such fingerprint in a Raman feature that was previously observed experimentally, thus providing direct spectroscopic confirmation of an ideal excitonic insulator phase in bulk [Formula: see text] above 30 GPa.

Frontier orbitals and quasiparticle energy levels in ionic liquids

Ionic liquids play an important role in many technological applications and a detailed understanding of their frontier molecular orbitals is required to optimize interfacial barriers, reactivity and stability with respect to electron injection and removal. In this work, we calculate quasiparticle energy levels of ionic liquids using first-principles many-body perturbation theory within the GW approximation and compare our results to various mean-field approaches, including semilocal and hybrid density-functional theory and Hartree–Fock. We find that the mean-field results depend qualitatively and quantitatively on the treatment of exchange–correlation effects, while GW calculations produce results that are in excellent agreement with experimental photoelectron spectra of gas phase ion pairs and ionic liquids. These results establish the GW approach as a valuable tool for understanding the electronic structures of ionic liquids.

Quasiparticle energies and excitonic effects of chromium trichloride: From two dimensions to bulk

Layered van der Waals (vdW) magnetic materials have attracted significant research interest to date. In this work, we employ the first-principles many-body perturbation theory to calculate excited-state properties of a prototype vdW magnet, chromium trichloride (CrCl3), covering monolayer, bilayer, and bulk structures. Unlike usual non-magnetic vdW semiconductors, in which many-electron interactions and excited states are sensitive to dimensionality, many-electron interactions are always enhanced and dominate quasiparticle energies and optical responses of both two-dimensional and bulk CrCl3. The electron-hole (e-h) binding energy can reach 3 eV in monolayer and remains as high as 2 eV in bulk. Because of the cancellation effect between self-energy corrections and e-h binding energies, the lowest-energy exciton (optical gap) is almost not affected by the change of dimensionality. Besides, for the excitons with similar e-h binding energies, their dipole oscillator strength can differ by a few orders of magnitude.Our analysis shows that such a big difference is from a unique interference effect between complex exciton wavefunctions and interband transitions. Finally, we find that the interlayer stacking sequence and magnetic coupling barely change quasiparticle band gaps and optical absorption spectra of CrCl3. Our calculated low-energy exciton peak positions agree with available measurements. These findings give insight into the understanding of many-electron interactions and the interplay between magnetic orders and optical excitations in vdW magnetic materials.

Plasmonic performance of AuxAgyCu1−x−y alloys from many-body perturbation theory

We present a detailed appraisal of the optical and plasmonic properties of ordered alloys of the form AuxAgyCu1-x-y, as predicted by means of first-principles many-body perturbation theory augmented by a semi-empirical Drude–Lorentz model. In benchmark simulations on elemental Au, Ag, and Cu, we find that the random-phase approximation (RPA) fails to accurately describe inter-band transitions when it is built upon semi-local approximate Kohn–Sham density-functional theory band-structures. We show that non-local electronic exchange-correlation interactions sufficient to correct this, particularly for the fully-filled, relatively narrow d-bands which contribute strongly throughout the low-energy spectral range (0–6 eV), may be modeled very expediently using band-stretching operators that imitate the effect of a perturbative self-energy correction incorporating quasiparticle (QP) mass renormalization. We thereby establish a convenient work-flow for carrying out approximated spectroscopic calculations on alloys and, in particular here, we have considered alloy concentrations down to 12.5% in , including all possible crystallographic orderings of face-centred cubic type. We develop a pragmatic procedure for calculating the Drude plasmon frequency from first principles, including self-energy effects, as well as a semi-empirical scheme for interpolating the plasmon inverse lifetimes between stoichiometries. A distinctive M-shaped profile is observed in both quantities for binary alloys, in qualitative agreement with previous experimental findings. A range of optical and plasmonic figures of merit are discussed, and plotted for ordered at three representative solid-state laser wavelengths. On this basis, we predict that certain compositions may offer improved performance over elemental Au for particular application types. We predict that while the loss functions for both bulk and surface plasmons are typically diminished in strength through binary alloying, certain stoichiometric ratios may exhibit higher-quality (longer-lived) localized surface-plasmons and surface-plasmon polaritons, at technologically-relevant wavelengths, than those in elemental Au.

Assessing the Role of Intermolecular Interactions in a Perylene-Based Nanowire Using First-Principles Many-Body Perturbation Theory.

We present a first-principles many-body perturbation theory study of the role of intermolecular coupling in the optoelectronic properties of a one-dimensional (1D) π-stacked nanowire composed of perylene-3,4,9,10-tetracarboxylic diimide molecules on a DNA-like backbone. We determine that strong intermolecular electronic coupling results in large bandwidths and low carrier effective masses, suggesting a high-electron mobility material. Additionally, by including the role of finite-temperature phonons on optical absorption via a newly presented approach, we predict that the optical absorption spectrum is significantly altered from that at zero temperature due to allowed indirect transitions, while the exciton delocalization and binding energy, a measure of intermolecular electronic interactions, remains constant. Overall, our studies indicate that strong intermolecular coupling can dominate the optoelectronic properties of π-conjugated 1D systems even at room temperature.

Optical vs electronic gap of hafnia by ab initio Bethe-Salpeter equation

We present first-principles many-body perturbation theory calculations of the quasiparticle electronic structure and the optical response of HfO2 polymorphs. We use the GW approximation including core electrons by the projector augmented wave method and performing a quasiparticle self-consistency also on wavefunctions. In addition, we solve the Bethe-Salpeter equation on top of GW to calculate optical properties including excitonic effects. For monoclinic HfO2, we find a fundamental bandgap of Eg = 6.33 eV (with the direct bandgap at Egd=6.41 eV) and an exciton binding energy of 0.57 eV, which situates the optical gap at Ego=5.85 eV. The latter is in the range of spectroscopic ellipsometry (SE) experimental estimates (5.5–6 eV), whereas our electronic bandgap is well beyond experimental photoemission (PE) estimates (<6 eV) and previous GW works. Our calculated density of states and optical absorption spectra compare well to raw PE and SE spectra. This suggests that our predictions of both optical and electronic gaps are close to, or at least lower bounds of, the real values.

Dependence of excited-state properties of tellurium on dimensionality: From bulk to two dimensions to one dimensions

The dependence of excited-state properties on dimensionality is the most prominent character of nanostructures. Using first-principles many-body perturbation theory, we show how those excited-state properties, i.e., quasiparticle energies and excitons, evolve with the dimensionality of tellurium nanostructures that have attracted significant interest because of their high carrier mobility and air stability. Even though the elementary atomistic structures are similar, dimensionality dictates many-electron interactions and excited-state properties: the self-energy correction to the band gap is increased from 0.22 eV in bulk to 0.90 eV in a two-dimensional (2D) monolayer, and ultimately to 2.70 eV in a one-dimensional (1D) spiral tube; excitonic effects are weak in bulk with an exciton binding energy less than 10 meV, while the exciton binding energy is substantially enhanced to be 0.67 eV in the monolayer and 2.40 eV in the 1D structure. Interestingly, reduced dimensionality also produces substantial anisotropic optical response through many-electron interactions: local-field effects dominate the optical spectra of 2D and 1D structures and induce highly anisotropic optical responses. These results not only reveal a systematic picture for understanding the evolution of excited-state properties with dimensionality but also suggest the possibility of designing macroscopic electronic and optical properties by engineering nanosized building blocks.

Quasiparticle band gaps and optical spectra of strained monolayer transition-metal dichalcogenides

Employing the first-principles many-body perturbation theory, we report the excited-state properties, i.e., quasiparticle energy and excitonic effects, of strained monolayer 2H-phase transition-metal dichalcogenides, including ${\mathrm{MoS}}_{2}, {\mathrm{MoSe}}_{2}, {\mathrm{WS}}_{2}$, and ${\mathrm{WSe}}_{2}$. Beyond previous studies that considered uniaxial or biaxial strain, we cover arbitrarily axial strains and find complicated variations of quasiparticle band gaps, band-edge energies, direct-indirect gap transitions, and exciton energies. These results provide a complete picture for straining engineering of electronic structures and optical spectra of two-dimensional transition-metal dichalcogenides. Particularly, combined with high spatial-resolution optical measurements, our calculated results are essential for identifying local strain distribution and understanding the widely observed inhomogeneous free-carrier distributions and photoluminescence in realistic two-dimensional materials.

Instantaneous band gap collapse in photoexcited monoclinic VO2 due to photocarrier doping.

Using femtosecond time-resolved photoelectron spectroscopy we demonstrate that photoexcitation transforms monoclinic VO2 quasi-instantaneously into a metal. Thereby, we exclude an 80 fs structural bottleneck for the photoinduced electronic phase transition of VO2. First-principles many-body perturbation theory calculations reveal a high sensitivity of the VO2 band gap to variations of the dynamically screened Coulomb interaction, supporting a fully electronically driven isostructural insulator-to-metal transition. We thus conclude that the ultrafast band structure renormalization is caused by photoexcitation of carriers from localized V 3d valence states, strongly changing the screening before significant hot-carrier relaxation or ionic motion has occurred.

Excitons in molecular crystals from first-principles many-body perturbation theory: Picene versus pentacene

By solving the first-principles many-body Bethe-Salpeter equation, we compare the optical properties of two prototype and technological relevant organic molecular crystals: picene and pentacene. Albeit very similar for the structural and electronic properties, picene and pentacene show remarkable differences in their optical spectra. While for pentacene the absorption onset is due to a charge-transfer exciton, in picene it is related to a strongly localized Frenkel exciton. The detailed comparison between the two materials allows us to discuss, on general grounds, how the interplay between the electronic band dispersion and the exchange electron-hole interaction plays a fundamental role in setting the nature of the exciton. It represents a clear example of the relevance of the competition between localization and delocalization in the description of two-particle electronic correlation.

Quasiparticle effects in the bulk and surface-state bands of Bi2Se3and Bi2Te3topological insulators

We investigate the bulk band structures and the surface states of Bi2Se3 and Bi2Te3 topological insulators using first-principles many-body perturbation theory based on the GW approximation. The quasiparticle self-energy corrections introduce significant changes to the bulk band structures, while their effect on the band gaps is opposite in the band-inversion regime compared to the usual situation without band inversion. Parametrized "scissors operators" derived from the bulk studies are then used to investigate the electronic structure of slab models which exhibit topologically protected surface states. The results including self-energy corrections reveal significant shifts of the Dirac points relative to the bulk bands and large gap openings resulting from the interactions between the surface states across the thin slab, both in agreement with experimental data.

Electronic Band Structures of ATaO3(A = Li, Na, and K) from First-Principles Many-Body Perturbation Theory

Alkaline tantalates, ATaO3 (A = Li, Na, and K), have attracted a lot of interest in recent years due to their interesting photocatalytic properties and their photocatalytic activity is influenced by a lot of factors, making them ideal model systems for in-depth theoretical investigation. In this work, electronic band structures of alkaline tantalates are investigated based on first-principles many-body perturbation theory in the GW approximation. The band gaps of NaTaO3 and KTaO3 from the GW approach agree very well with experiment; on the other hand, the band gap of LiTaO3 from GW is significantly larger than the experimental values. A strong dependence on crystal structures is observed in LiTaO3, whose band gap in the cubic and rhombohedral structure differs by more than 1.5 eV. Combined with the phenomenological ionic model, it is found that both the Madelung potential and the bandwidth can have strong influences on the band gap. By comparing the structure dependence of LiTaO3 and NaTaO3, it is conclud...