Exciton Absorption Spectra Research Articles

Effects of non-resonant intense laser, electric and magnetic fields on exciton binding energy and absorption spectra in the Gaussian double quantum well

Effects of non-resonant intense laser, electric and magnetic fields on exciton binding energy and absorption spectra in the Gaussian double quantum well

Excitons, optical spectra, and electronic properties of semiconducting Hf-based MXenes.

Semiconducting MXenes are an intriguing two-dimensional (2D) material class with promising electronic and optoelectronic properties. Here, we focused on recently prepared Hf-based MXenes, namely, Hf3C2O2 and Hf2CO2. Using the first-principles calculation and excited state corrections, we proved their dynamical stability, reconciled their semiconducting behavior, and obtained fundamental gaps by using the many-body GW method (indirect 1.1 and 2.2eV; direct 1.4 and 3.5eV). Using the Bethe-Salpeter equation, we subsequently provided optical gaps (0.9 and 2.7eV, respectively), exciton binding energies, absorption spectra, and other properties of excitons in both Hf-based MXenes. The indirect character of both 2D materials further allowed for a significant decrease of excitation energies by considering indirect excitons with exciton momentum along the Γ-M path in the Brillouin zone. The first bright excitons are strongly delocalized in real space while contributed by only a limited number of electron-hole pairs around the M point in the k-space from the valence and conduction band. A diverse range of excitonic states in Hf3C2O2 MXene lead to a 4% and 13% absorptance for the first and second peaks in the infrared region of absorption spectra, respectively. In contrast, a prominent 28% absorptance peak in the visible region appears in Hf2CO2 MXene. Results from radiative lifetime calculations indicate the promising potential of these materials in optoelectric devices requiring sustained and efficient exciton behavior.

Exciton and biexciton transient absorption spectra of CdSe quantum dots with varying diameters.

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton.

Quantum Size Effect in Three-Dimensional Microscopic Semiconductor Crystals

The exciton absorption spectrum of microscopic CuCl crystals grown in a transparent dielectric matrix has been studied. The size of the microscopic crystals was varied in a controlled manner from several tens of angstroms to hundreds of angstroms. There is a short-wave shift (of up to 0.1 eV) of the exciton absorption lines, caused by a quantum size effect.

Exciton absorption spectrum of thin films of ternary compounds in the CsCl–CuCl system

The absorption spectra of thin films (CsCl)1–x(CuCl)x were studied at T = 90 K in the spectral range 2–6 eV. From the analysis of the spectra, the formation of CsCu2Cl3 and Cs2CuCl3 compounds in the CsCl–CuCl system was created. The Cs2CuCl3 compound is stable only in a vacuum; in air, it apparently decomposes into CsCu2Cl3 with a disordered crystal lattice and CsCl. The exciton spectrum of both compounds is interpreted on the basis of transitions in the Cu+ ion. The one-dimensional character of excitons in CsCu2Cl3 and the two-dimensional character in Cs2CuCl3 were established.

Exploring the photovoltaic properties of promising non-fullerene acceptors with different degrees of asymmetry due to halogenations of terminal groups

Over the past few years, the strategy of asymmetric modification has become popular for designing new photovoltaic materials because it can effectively improve optoelectronic performance and morphology, therefore power conversion efficiency (PCE). However, how the halogenations (to further change asymmetry) of terminal groups (TGs) of an asymmetric small-molecule non-fullerene acceptor (Asy-SM-NFA) influence optoelectronic properties is still not very clear. In this work, we have selected a promising Asy-SM-NFA IDTBF (the OSC based on it has a PCE of 10.43 %), exacerbated the asymmetry through fluorinations of TGs, and finally designed six new molecules. Based on density functional theory (DFT) and time-dependent DFT calculations, we systematically examine how the changed asymmetry impacts the optoelectronic properties. We find that the halogenations of TGs may significantly affect the molecular planarity, dipole moment, electrostatic potential, exciton binding energy, energy loss, and absorption spectrum. And the results show that newly designed BR-F1 and IM-mF (m = 1,3, and 4) are potential Asy-SM-NFAs because they all have enhanced absorption spectra in the visible region. Therefore, we provide a meaningful direction for the design of asymmetric NFA.

Thermal effect on magnetoexciton energy spectra in monolayer transition metal dichalcogenides

It is widely comprehended that temperature may cause phonon-exciton scattering, enhancing the energy level's linewidth and leading to some spectrum shifts. However, in the present paper, we suggest a different mechanism that allows the thermal motion of the exciton's center of mass (c.m.) to affect the magnetoexciton energies in monolayer dichalcogenides (TMDCs). By the nontrivial but precise separation of the c.m. motion from an exciton in a monolayer TMDC with a magnetic field, we obtain an equation for the relative motion containing a motional Stark term proportional to the c.m. pseudomomentum, related to the temperature of the exciton gas but neglected in the previous studies. Solving the Schr\"odinger equation without omitting the motional Stark potential at room temperature shows approximately a few meV thermal-magnetic shifts in the exciton energies, significant enough for experimental detection. Moreover, this thermal effect causes a change in exciton radius and diamagnetic coefficient and enhances the exciton lifetime as a consequence. Surprisingly, the thermoinduced motional Stark potential breaks the system's SO(2) symmetry, conducting new peaks in the exciton absorption spectra at room temperature besides those of the $s$ states. This mechanism could be extended for other magnetoquasiparticles such as trions and biexcitons.

Excitons and Their Fine Structure in Lead Halide Perovskite Nanocrystals from Atomistic GW/BSE Calculations

Atomistically detailed computational studies of nanocrystals, such as those derived from the promising lead-halide perovskites, are challenging due to the large number of atoms and lack of symmetries to exploit. Here, focusing on methylammonium lead iodide nanocrystals, we combine a real-space tight binding model with the GW approximation to the self-energy and obtain exciton wave functions and absorption spectra via solutions of the associated Bethe–Salpeter equation. We find that the size dependence of carrier confinement, dielectric contrast, electron–hole exchange, and exciton binding energies has a strong impact on the lowest excitation energy, which can be tuned by almost 1 eV over the diameter range of 2–6 nm. Our calculated excitation energies are about 0.2 eV higher than experimentally measured photoluminescence, and they display the same qualitative size dependence. Focusing on the fine structure of the band-edge excitons, we find that the lowest-lying exciton is spectroscopically dark and about 20–30 meV lower in energy than the higher-lying triplet of the bright states whose degeneracy is slightly broken by crystal field effects.

Anisotropic exciton states and excitonic absorption spectra in a freestanding monolayer black phosphorus

The anisotropic exciton states and excitonic absorption spectra in a freestanding monolayer black phosphorus (BP) are theoretically investigated by a variationally optimized diagonalization method based on a two-dimensional (2D) nonorthogonal Laguerre basis. The exciton Hamiltonian works in the anisotropic form of the kinetic term, which has an advantage of a fully analytical expression for the matrix elements of the Hamiltonian. The energy of 1 s state is in good agreement with the reported result based on the Numerov approach. The exciton states are elongated along the x direction, while their radial nodes occur in the y direction, which leads to anomalous anisotropy in some excited states. The excitonic absorption spectra of monolayer BP possess highly anisotropic features and more peaks. The large anisotropy of the effective masses leads to the mixture of exciton states with different quantum numbers n and l , which results in highly nonhydrogenic and anisotropic features. These unusual excitonic and optical properties demonstrate the potential applications of monolayer BP in optoelectronics. Compared with my proposed diagonalization method, the variational method presented in the literatures is not a good approximation. My proposed variationally optimized diagonalization method based on a 2D nonorthogonal Laguerre basis is proven to be efficient and reliable in calculating highly accurate exciton states of anisotropic 2D materials . • A fully analytical expression of the matrix elements of the Hamiltonian is obtained. • The energy of 1 s state is in good agreement with the reported result based on the Numerov approach. • The states are elongated along the x direction while radial nodes occur in the y direction. • The excitonic absorption spectra possess highly anisotropic features and more peaks. • A 2D nonorthogonal Laguerre basis is efficient and reliable in calculating exciton states of anisotropic materials.

Translation-Invariant Excitons in a Phonon Field

Large-radius excitons in polar crystals are considered. It is shown that translation invariant description of excitons interacting with a phonon field leads to a nonzero contribution of phonons into the exciton ground state energy only in the case of weak or intermediate electron-phonon coupling. A conclusion is made that self-trapped excitons cannot exist in the limit of strong coupling. Peculiarities of the absorption and emission spectra of translation invariant excitons in a phonon field are discussed. Conditions when the hydrogen-like exciton model remains valid in the case of electron-phonon interaction are found.

Exciton absorption spectra of thin films of RbCu2Cl3 and Rb2Cu3Cl5 ternary compounds

The absorption spectra of RbCu2Cl3 and Rb2Cu3Cl5 thin films were studied in the 2−6 eV spectral and 90−450 K temperature ranges. The localization of excitons in CuCl43− structural elements of crystal lattice of compounds, three-dimensional nature of excitons in RbCu2Cl3 and two-dimensional nature of excitons in Rb2Cu3Cl5 were established. The exciton spectra of RbCu2Cl3 and Rb2Cu3Cl5 thin films were interpreted based on the transitions in the Cu+ ion.

On the Optical Stark Effect of Excitons in InGaAs Prolate Ellipsoidal Quantum Dots

In this paper, we study the exciton absorption spectra in InGaAs prolate ellipsoidal quantum dots when a strong pump laser resonant with electron quantized levels is active. Our obtained results by renormalized wavefunction theory show that, under suitable conditions, the initial exciton absorption peak is split into two new peaks as the evidence of the existence of the three-level optical Stark effect of excitons. We have suggested an explanation of the origin of the effect as well as investigating the effect of pump field energy, size, and geometric shape of the quantum dots on effect characteristics. The comparison with the results obtained in the spherical quantum dots implies the important role of geometric shape of the quantum structures when we examine this effect.

Three-Level Optical Stark Effect of Excitons in GaAs Cylindrical Quantum Wires

This study looks at the three-level optical Stark effect of excitons in GaAs cylindrical quantum wires, utilizing the renormalized wave function theory. By applying the three-level model consisting of the first two electron levels connected via a powerful pump laser and the first hole level, we observe the appearance of the excitonic optical Stark effect through the appearance of two separated peaks in the exciton absorption spectra. In addition, the strong impact of the pump laser detuning and the wire radius on the optical Stark effect are also put under thorough examination. Finally, a brief guidance for experimental verification is also suggested.

Donor−acceptor−donor (D-A-D) structural monomers as donor materials in polymer solar cells: a DFT/TDDFT approach

ABSTRACT Density functional theory (DFT) and time-dependent DFT (TD-DFT) are used to investigate the ground- and excited-state properties of donor-acceptor–donor (D-A-D) monomers based on 3,6-carbazole (CB) combined with various-conjugated benzothiazole derivatives, using B3LYP and the 6–311 G basis set. To create nine D-A-D monomers for this investigation, nine (9) distinct acceptors were inserted at the C3 and C6 positions of carbazole. The impact of various electron-donor groups on structural, electrical, and optoelectronic properties is investigated. Our technique for developing novel donor monomers provides a theoretical framework for further optimizing the photovoltaic device’s electrical, optical, and efficiency features. The HOMO and LUMO energies, bandgap, excited state, exciton binding energy, open-circuit voltage (VOC) and absorption spectra were calculated. Our findings indicate that CB-TDP-CB and CB-SDP-CB monomers have an appropriate electronic structure for polymer solar cells.

A colloquium on the variational method applied to excitons in 2D materials

In this colloquium, we review the research on excitons in van der Waals heterostructures from the point of view of variational calculations. We first make a presentation of the current and past literature, followed by a discussion on the connections between experimental and theoretical results. In particular, we focus our review of the literature on the absorption spectrum and polarizability, as well as the Stark shift and the dissociation rate. Afterwards, we begin the discussion of the use of variational methods in the study of excitons. We initially model the electron-hole interaction as a soft-Coulomb potential, which can be used to describe interlayer excitons. Using an \emph{ansatz}, based on the solution for the two-dimensional quantum harmonic oscillator, we study the Rytova-Keldysh potential, which is appropriate to describe intralayer excitons in two-dimensional (2D) materials. These variational energies are then recalculated with a different \emph{ansatz}, based on the exact wavefunction of the 2D hydrogen atom, and the obtained energy curves are compared. Afterwards, we discuss the Wannier-Mott exciton model, reviewing it briefly before focusing on an application of this model to obtain both the exciton absorption spectrum and the binding energies for certain values of the physical parameters of the materials. Finally, we briefly discuss an approximation of the electron-hole interaction in interlayer excitons as an harmonic potential and the comparison of the obtained results with the existing values from both first--principles calculations and experimental measurements.

The two light-harvesting membrane chromoproteins of Thermochromatium tepidum expose distinct robustness against temperature and pressure

An increased robustness against high temperature and the much red-shifted near-infrared absorption spectrum of excitons in the LH1-RC core pigment-protein complex from the thermophilic photosynthetic purple sulfur bacterium Thermochromatium tepidum has recently attracted much interest. In the present work, thermal and hydrostatic pressure stability of the peripheral LH2 and core LH1-RC complexes from this bacterium were in parallel investigated by various optical spectroscopy techniques applied over a wide spectral range from far-ultraviolet to near-infrared. In contrast to expectations, very distinct robustness of the complexes was established, while the sturdiness of LH2 surpassed that of LH1-RC both with respect to temperatures between 288 and 360 K, and pressures between 1 bar and 14 kbar. Subtle structural variances related to the hydrogen bond network are likely responsible for the extra stability of LH2.

Dielectric Confinement Enables Molecular Coupling in Stacked Colloidal Nanoplatelets.

We show theoretically that carriers confined in semiconductor colloidal nanoplatelets (NPLs) sense the presence of neighbor, cofacially stacked NPLs in their energy spectrum. When approaching identical NPLs, the otherwise degenerate energy levels red-shift and split, forming (for large stacks) minibands that are several millielectronvolts in width. Unlike in epitaxial structures, the molecular behavior does not result from quantum tunneling but from changes in the dielectric confinement. The associated excitonic absorption spectrum shows a rich structure of bright and dark states, whose optical activity and multiplicity can be understood from reflection symmetry and Coulomb tunneling. We predict spectroscopic signatures that should confirm the formation of molecular states, whose practical realization would pave the way for the development of nanocrystal chemistry based on NPLs.

Tailoring Hot Exciton Dynamics in 2D Hybrid Perovskites through Cation Modification

We report a family of two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead iodide ((PEA)2PbI4) that show complex structure in their low-temperature excitonic absorption and photoluminescence (PL) spectra as well as hot exciton PL. We replace the 2-position (ortho) H on the phenyl group of the PEA cation with F, Cl, or Br to systematically increase the cation's cross-sectional area and mass and study changes in the excitonic structure. These single atom substitutions substantially change the observable number of and spacing between discrete resonances in the excitonic absorption and PL spectra and drastically increase the amount of hot exciton PL that violates Kasha's rule by over an order of magnitude. To fit the progressively larger cations, the inorganic framework distorts and is strained, reducing the Pb-I-Pb bond angles and increasing the 2DHP band gap. Correlation between the 2DHP structure and steady-state and time-resolved spectra suggests the complex structure of resonances arises from one or two manifolds of states, depending on the 2DHP Pb-I-Pb bond angle (as)symmetry, and the resonances within a manifold are regularly spaced with an energy separation that decreases as the mass of the cation increases. The uniform separation between resonances and the dynamics that show excitons can only relax to the next-lowest state are consistent with a vibronic progression caused by a vibrational mode on the cation. These results demonstrate that simple changes to the cation can be used to tailor the properties and dynamics of the confined excitons without directly modifying the inorganic framework.

Spatially asymmetric transients of propagating exciton-polariton modes in a planar CdZnTe/CdMgTe guiding structure

We report on ultrafast time-resolved pump-probe studies in a CdZnTe/CdMgTe planar guiding structure covered with a metallic grating. The one-dimensional periodic gold structure allows for efficient coupling into the guiding layer for $p$-polarized 30 fs optical pulses with a large spectral bandwidth of about 60 nm. The resulting spectral width of optical pulses propagating inside the guiding layer corresponds to 20--30 nm. We demonstrate that the excitation of exciton-polariton modes in the guiding layer leads to a modulation of the optical response in the vicinity of the excitonic resonance. Spatially resolved pump-probe measurements show an asymmetric behavior in the optical response when the relative position of the pump and probe spots is varied on the scale of ten micrometers perpendicular to the metal ridges. This is attributed to the excitation of resonant and off-resonant exciton-polariton modes which propagate in opposite directions inside the guiding layer in accordance with their dispersion relations. Two main mechanisms are considered and evaluated, namely, Pauli blocking and excitation-induced dephasing, which are shown to be responsible for the pump-induced changes in the exciton absorption spectrum. While both of these processes lead to the generation of photoexcited carriers in the guiding layer, their impact on the optical properties (transmission and reflection) are different which leads to the asymmetric behavior of the spatially resolved transients.

Influence of electron-hole plasma on Rydberg excitons in cuprous oxide

We develop a many-body approach to the behavior of exciton bound states and the conduction electron band edge in a surrounding electron-hole plasma with a focus on the absorption spectrum of Rydberg excitons in cuprous oxide. The interplay of band edge and exciton levels is analyzed numerically, whereby the self-consistent solution is compared to the semiclassical Debye approximation. Our results provide criteria which allow to verify or rule out the different band edge models against future experimental data.