Wannier Excitons Research Articles

Theory of high-temperature superfluorescence in hybrid perovskite thin films.

The recent discovery of high-temperature superfluorescence in hybrid perovskite thin films has opened new possibilities for harnessing macroscopic quantum phenomena in nanotechnology. This study aimed to elucidate the mechanism that enables high-temperature superfluorescence in these systems. The proposed model describes a quasi-2D Wannier exciton in a thin film that interacts with phonons via the longitudinal optical phonon-exciton Fröhlich interaction. We show that the super-radiant properties of the coherent state in hybrid perovskites are stable against perturbations caused by the longitudinal optical phonon-exciton Fröhlich interaction. Using the multiconfiguration Hartree approach, we derive semiclassical equations of motion for a single-exciton wavefunction, where the vibrational degrees of freedom interact with the Wannier exciton through a mean-field Hartree term. Super-radiance is effectively described by a non-Hermitian term in the Hamiltonian. The analysis was then extended to multiple excited states using the semiclassical Hamiltonian as the basic model. We demonstrate that the ground state of the model exciton Hamiltonian with long-range interactions is a symmetric Dicke super-radiant state, where the Fröhlich interaction is nullified. The additional density matrix-based consideration draws an analogy between this system and stable systems, where the conservation laws determine the nullification of the constant (momentum-independent) decay rate part. In the exciton-phonon system, nullification is associated with the absence of a momentum-independent component in the Wannier exciton-phonon interaction coupling function.

Phonon-Mediated Exciton Relaxation in Two-Dimensional Semiconductors: Selection Rules and Relaxation Pathways.

Exciton-phonon coupling (ExPC) is crucial for energy relaxation in semiconductors, yet the first-principles calculation of such coupling remains challenging, especially for two-dimensional (2D) systems. Here, an accurate method for calculating ExPC is developed and applied in exciton relaxation problems in monolayer WSe2. Considering the interplay between the exciton wave functions and electron-phonon coupling (EPC) matrix elements, we find that ExPC shows selection rules distinct from the ones of EPC. By employing the Wannier exciton model, we generalize these selection rules, which state that the angular quantum numbers of the exciton must match the winding numbers of the EPC matrix elements for the ExPC to be allowed. To verify our theory and method, we calculate intervalley exciton relaxation pathways, which agree well with a recent experiment.

Excitonic Properties versus Structure Stability Trade‐Off in Halide Perovskite Photovoltaics Caused by van der Waals Interactions

Lead halide perovskites, and their derivatives, are among the most promising photovoltaic materials for third generation solar cells. Despite the large number of available works on some of these materials, excitonic properties whose assessment has been challenging are less investigated. These include quantitative measures of excitonic properties variations with van der Waals (vdW) interactions. Consistent comparisons of how vdW interactions affect phononic and optical properties are also desirable. This work focuses on cubic phases of with X = Cl, Br, I, and MA = methylammonium, using density functional theory simulations including vdW interactions. These cause 30%–38% increase of absolute cohesive energies and 15%–37% reduction of ionic/vibrational contributions to static dielectric constants, along with 10%–29% reduction of exciton Bohr radii and 29%–107% increase of exciton binding energies. The effects on band gaps, frequency‐dependent dielectric functions, and exciton effective masses are less pronounced. Within the Mott–Wannier exciton model, the results suggest a trade‐off between photovoltaic performance and structure stability. The results can help assess stability, feasibility, and performance of hybrid photovoltaic materials.

Strongly Bound Frenkel Excitons on TiO2 Nanoparticles: An Evolutionary and DFT Approach

An evolutionary algorithm was employed to locate the global minimum of TiO2n nanoparticles with n=2–20. More than 61,000 structures were calculated with a semiempirical method and reoptimized using density functional theory. The exciton binding energy of TiO2 nanoparticles was determined through the fundamental and optical band gap. Frenkel exciton energy scales as EB eV=8.07/n0.85, resulting in strongly bound excitons of 0.132–1.2 eV for about 1.4 nm nanoparticles. Although the exciton energy decreases with the system size, these tightly bound Frenkel excitons inhibit the separation of photogenerated charge carriers, making their application in photocatalysis and photovoltaic devices difficult, and imposing a minimum particle size. In contrast, the exciton binding energy of rutile is 4 meV, where the Wannier exciton energy scales as EB eV=13.61 μ/ε2. Moreover, the Wannier excitons in bulk TiO2 are delocalized according to the Bohr radii: 3.9 nm for anatase and 7.7 nm for rutile.

Disorder on Mixed Cation Halide Perovskite for Photovoltaic Applications.

With reduced toxicity and tunable optoelectronic properties, mixed cation halide perovskites (MCHPs) featuring partially substituted Pb with Sn and Ge have emerged as promising candidates for photovoltaic applications. However, the introduction of the disorder through large-scale preparation and alloying strategies leads to a significant challenge in comprehending the disorder's microscopic-level impact. Here, we found that, in addition to compositional variation, a synergy of disorder and cation radii ratio significantly affects optoelectronic properties. For Pb-Ge/Ge-Sn MCHPs, severe octahedral distortion with increasing degree of disorder adjusted their bandgaps in a wide range, giving rise to large effective masses, exciton binding energies, and weak visible absorption coefficients. The synergy of disorder and distortion transforms the Wannier excitons into localized characteristics, whereas the optoelectronic properties of Pb-Sn MCHPs are modulated by the disorder. Our work highlights the role of disorder in the tunability of optoelectronic properties, providing a novel strategy for designing photovoltaic materials.

Photoexcitation of planar Wannier excitons by twisted photons

Photoexcitation of planar Wannier excitons by twisted photons in thin semiconductor films is investigated. The excitons are assumed to be already created. The explicit general formulas for transition probabilities between exciton states are derived. The selection rules for the projection of the total angular momentum are obtained. As examples, the Coulomb and Rytova–Keldysh electron–hole interaction potentials are considered. The use of planar excitons as a pure on-chip source of twisted photons is discussed. The formulas obtained also describe photoexcitation of states of electrons and holes bound to charged impurities in planar semiconductors.

Single-particle properties of topological Wannier excitons in bismuth chalcogenide nanosheets

We analyze the topology, dispersion, and optical selection rules of bulk Wannier excitons in nanosheets of Bi2Se3, a topological insulator in the family of the bismuth chalcogenides. Our main finding is that excitons also inherit the topology of the electronic bands, quantified by the skyrmion winding numbers of the constituent electron and hole pseudospins as a function of the total exciton momentum. The excitonic bands are found to be strongly indirect due to the band inversion of the underlying single-particle model. At zero total momentum, we predict that the s-wave and d-wave states of two exciton families are selectively bright under left- or right-circularly polarized light. We furthermore show that every s-wave exciton state consists of a quartet with a degenerate and quadratically dispersing nonchiral doublet, and a chiral doublet with one linearly dispersing mode as in transition metal dichalcogenides. Finally, we discuss the potential existence of topological edge states of chiral excitons arising from the bulk-boundary correspondence.

Improved quasiparticle self-consistent electronic band structure and excitons in β−LiGaO2

The band structure of $\beta$-LiGaO$_2$ is calculated using the quasiparticle self-consistent QS$G\hat W$ method where the screened Coulomb interaction $\hat W$ is evaluated including electron-hole interaction ladder diagrams and $G$ is the one-electron Green's function. Improved convergence compared to previous calculations leads to a significantly larger band gap of about 7.0 eV. However, exciton binding energies are found to be large and lead to an exciton gap of about 6.0 eV if also a zero-point-motion correction of about $-0.4$ eV is included. These results are in excellent agreement with recent experimental results on the onset of absorption. Besides the excitons observed thus far, the calculations indicate the existence of a Rydberg-like series of exciton excited states, which is however modified from the classical Wannier exciton model by the anisotropies of the material and the more complex mixing of Bloch states in the excitons resulting from the Bethe-Salpeter equation. The exciton fine structure and the exciton wave functions are visualized and analyzed in various ways.

Wannier excitons confined in hexagonal boron nitride triangular quantum dots

With the ever-growing interest in quantum computing, understanding the behavior of excitons in monolayer quantum dots has become a topic of great relevance. In this paper, we consider a Wannier exciton confined in a triangular quantum dot of hexagonal boron nitride. We begin by outlining the adequate basis functions to describe a particle in a triangular enclosure, analyzing their degeneracy and symmetries. Afterwards, we discuss the excitonic Hamiltonian inside the quantum dot and study the influence of the quantum dot dimensions on the excitonic states.

Phase relaxation control in heterostructures featuring charge-transfer excitons

Type-II quantum well heterostructures are considered high-potential candidates for next-generation active semiconductor devices. They promise low fundamental transition energies and suppressed Auger scattering as well as temperature stability in device performance. Understanding their fundamental properties, such as scattering and diffusion, and revealing intricate differences from type-I quantum structures are important steps towards optimized structure design. Using degenerate four-wave mixing spectroscopy, we investigate the phase coherence of excitonic polarizations in a (Ga,In)As/GaAs/Ga(As,Sb) type-II double-quantum-well structure. It is designed to exhibit spectrally isolated resonances in its linear absorption spectrum including a well-resolved charge-transfer exciton resonance. This allows us to study the coherent dynamics of the unperturbed charge-transfer exciton polarization. In addition, the effects of many-body interactions with free charge carriers as well as excitons that are injected by an optical prepulse are revealed. Scattering of charge-transfer excitons with free charge carriers is three times more efficient than scattering of charge-transfer excitons with each other. The comparison with Wannier excitons in a type-I quantum well structure shows that the interaction strength between charge-transfer excitons is about twice as large as for excitons in a type-I quantum well structure.

Synthesis of Weakly Confined, Cube-Shaped, and Monodisperse Cadmium Chalcogenide Nanocrystals with Unexpected Photophysical Properties.

Zinc-blende CdSe, CdS, and CdSe/CdS core/shell nanocrystals with a structure-matched shape (cube-shaped, edge length ≤30 nm) are synthesized via a universal scheme. With the edge length up to five times larger than exciton diameter of the bulk semiconductors, the nanocrystals exhibit novel properties in the weakly confined size regime, such as near-unity single exciton and biexciton photoluminescence (PL) quantum yields, single-nanocrystal PL nonblinking, mixed PL decay dynamics of exciton and free carriers with sub-microsecond monoexponential decay lifetime, and stable yet extremely narrow PL full width at half maximum (FWHM < 0.1 meV) at 1.8 K. Their monodisperse edge length, shape, and facet structure enable demonstration of unexpected yet size-dependent PL properties at room temperature, including unusually broad and abnormally size-dependent PL FWHM (∼100 meV), nonmonotonic size dependence of PL peak energy, and dual-peak single-exciton PL. Calculations suggest that these unusual properties should be originated from the band-edge electron/hole states of the dynamic-exciton, whose exciton binding energy is too small to hold the photogenerated electron-hole pair as a bonded Wannier exciton in a weakly confined nanocrystal.

Intralayer charge-transfer moiré excitons in van der Waals superlattices.

Moiré patterns of transition metal dichalcogenide heterobilayers have proved to be an ideal platform on which to host unusual correlated electronic phases, emerging magnetism and correlated exciton physics. Whereas the existence of new moiré excitonic states is established1-4 through optical measurements, the microscopic nature of these states is still poorly understood, often relying on empirically fit models. Here, combining large-scale first-principles GW (where G and W denote the one-particle Green's function and the screened Coulomb interaction, respectively) plus Bethe-Salpeter calculations and micro-reflection spectroscopy, we identify the nature of the exciton resonances in WSe2/WS2 moiré superlattices, discovering a rich set of moiré excitons that cannot be captured by prevailing continuum models. Our calculations show moiré excitons with distinct characters, including modulated Wannier excitons and previously unidentified intralayer charge-transfer excitons. Signatures of these distinct excitonic characters are confirmed experimentally by the unique carrier-density and magnetic-field dependences of different moiré exciton resonances. Our study highlights the highly non-trivial exciton states that can emerge in transition metal dichalcogenide moiré superlattices, and suggests new ways of tuning many-body physics in moiré systems by engineering excited-states with specific spatial characters.

A scenario for high-temperature excitonic insulators

While excitonic insulators (EIs) have been intensively studied, proper platforms of them with stable lattice and non-cryogenic T C are rare. By analysing their Bardeen–Cooper–Schieffer-like gap equation, we propose that high T C EIs can exist in small indirect band gap 2D materials. After screening 2D transition-metal dichalcogenides from existing computational works, we select 2H-TiTe2 and 1T-PdTe2, and show that their T C can be as high as 150 to 200 K under strains. A transition of their condensate EI state from that composed by Wannier excitons to that composed by plasmonic ones exists, even if negligible changes are reflected by the EI band structures, demonstrating the rich quantum feature of these systems. The high T C also implies that they are ideal platforms for the demonstration and applications of EIs and their related quantum states in non-cryogenic environments.

Franz-Keldysh and Stark Effects in Two-Dimensional Metal Halide Perovskites

The established theory of a two-dimensional (2D) Wannier exciton in a uniform electric field is used to analyze the electroabsorption response of an archetypal 2D metal halide perovskite (MHP), phenethylammonium lead iodide. The high level of agreement between the electroabsorption simulation and measurement allows for a deepened understanding of the redshift of exciton energy, according to the quadratic Stark effect, and the continuum wave function leaking, according to the Franz-Keldysh effect. We find the field dependency of each of these effects to be rich with information, yielding measurements of the exciton Bohr radius, transition dipole moment, polarizability, and reduced effective mass of the exciton. Most importantly, the band-gap energy and exciton binding energy are unambiguously determined with 1σ variance of 4 meV. The high precision of these new measurement methods opens the opportunity for determining the influence of chemical and environmental factors on the optoelectronic properties of MHPs, which would enable the fabrication of highly efficient and reproducible light-harvesting and light-emitting optoelectronic devices.8 MoreReceived 21 September 2021Revised 22 December 2021Accepted 2 February 2022DOI:https://doi.org/10.1103/PRXEnergy.1.013001Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasStark effectPhysical SystemsPerovskitesQuantum wellsTechniquesOptical absorption spectroscopyCondensed Matter, Materials & Applied Physics

Coherently degenerate state engineering of organic small molecule materials to generate Wannier excitons

Engineering organic small molecule materials capable of generating Wannier excitons is a pinnacle of research for organic optoelectronic devices. In this work, we used a coherently degenerate state strategy to design and synthesize an organic small molecule dimer compound consisting of two triphenylamine based monomers. A technique was developed to identify the coherently degenerate states in the dimer compound from the results of density functional theory calculations of. The time-resolved fluorescence measurements showed that the lifetime of the Wannier excitons in the newly designed dimer compound is less solvent dependent than that of the Frenkel excitons in the monomer. The power conversion efficiency of the photovoltaics constructed using this new material increases by 8-fold in comparison to that using the monomer. The method developed here offers extraordinary opportunities for rational design of organic materials to generate Wannier excitons.

Effect of phononic and electron collisional interaction on temperature dependent exciton radiation dynamics of doped GaN

In ultraviolet light emission devices, excitons are a high-efficiency emission source. However, the mechanism of experimentally observed dependence of excitonic radiative lifetimes on temperature (T) has not been discovered. We present a numerical simulation based on the phonon-exciton-radiation system, which reveals that the dependence of the radiative lifetime of GaN excitons on T is dominated by the population distribution among discrete and continuum energy states. This finding is in contrast to an existing model considering the existence of 1S exciton only. This population distribution is determined by the temperature-dependent integrated effect of background carrier density and exciton energy broadening, which induces a combination of high-order excitonic states and the continuum. Various experimental results on the dependence on temperature, including the functions of T3/2 and higher or lower power of T, are interpreted by a model integrating the interactions with the electron and phononic fields. The proposed model elucidates the corresponding effects of electronic and phononic processes in this complex system and provides a platform for the discussion of Wannier exciton dynamics under various thermal conditions, including nonequilibrium cases beyond the Saha-Boltzmann relation in population distribution.

Reviving modulational instability with third-order dispersion

It is well-known that third-order dispersion (TOD) plays no role in the onset of modulation instability in the nonlinear Schrödinger (NLS) family of systems. Here we demonstrate that the characteristics of modulational instability can be dramatically altered by the TOD in two different nonlinear systems, namely Wannier exciton mass in a ZnCdSe/ZnSe semiconductor superlattice and nonlinear pulse/beam propagation in a Kerr-like waveguide under non-slowly varying envelope approximation (non-SVEA), with spatial dispersion. Further we reveal the results of numerical simulations suggesting the existence of recently much studied Akhmediev-type breathers and Peregrine-like rogue waves due to the nonlinear development of MI stemming from the TOD.

Circularly Polarized Photoluminescence from Chiral Perovskite Thin Films at Room Temperature.

Hybrid organic-inorganic perovskites allow the synthesis of high-quality, nanostructured semiconducting films via easily accessible solution-based techniques. This has allowed tremendous development in optoelectronic applications, primarily solar cells and light-emitting diodes. Allowed by the ease of access to nanostructure, chirality has recently been introduced in semiconducting perovskites as a promising way to obtain advanced control of charge and spin and for developing circularly polarized light sources. Circular polarization of photoluminescence (CPL) is a powerful tool to probe the electronic structure of materials. However, CPL in chiral perovskites has been scarcely investigated, and a study in bulk thin films and at room temperature is still missing. In this work, we fabricate bromine-based chiral perovskites by using a bulky chiral organic cation mixed with CsBr, resulting in Ruddlesden-Popper perovskite thin films. We measure CPL on these films at room temperature and, by using unpolarized photoexcitation, we record a degree of circular polarization of photoluminescence in the order of 10-3 and provide a full spectral characterization of CPL. Our results show that chirality is imparted on the electronic structure of the semiconductor; we hypothesize that the excess in polarization of emitted light originates from the charge in the photogenerated Wannier exciton describing an orbit in a symmetry-broken environment. Furthermore, our experiments allow the direct measurement of the magnetic dipole moment of the optical transition, which we estimate to be ≥0.1 μB. Finally, we discuss the implications of our findings on the development of chiral semiconducting perovskites as sources of circularly polarized light.

Mahan excitons in room-temperature methylammonium lead bromide perovskites

In a seminal paper, Mahan predicted that excitonic bound states can still exist in a semiconductor at electron-hole densities above the insulator-to-metal Mott transition. However, no clear evidence for this exotic quasiparticle, dubbed Mahan exciton, exists to date at room temperature. In this work, we combine ultrafast broadband optical spectroscopy and advanced many-body calculations to reveal that organic-inorganic lead-bromide perovskites host Mahan excitons at room temperature. Persistence of the Wannier exciton peak and the enhancement of the above-bandgap absorption are observed at all achievable photoexcitation densities, well above the Mott density. This is supported by the solution of the semiconductor Bloch equations, which confirms that no sharp transition between the insulating and conductive phase occurs. Our results demonstrate the robustness of the bound states in a regime where exciton dissociation is otherwise expected, and offer promising perspectives in fundamental physics and in room-temperature applications involving high densities of charge carriers.

Temperature-dependent anomalous dispersion of polycrystalline germanium film near absorption threshold

Temperature-dependent refractive index of semiconductor germanium (Ge) near the absorption threshold has not been well studied theoretically and experimentally up to now. This paper presents a study of the temperature-dependent refractive index of Ge film near its absorption threshold (about 0.8 eV or 1550 nm), whose values deduced from the reflectivity and transmissivity of high crystalline Ge film fabricated on a fiber tip. Different from previous reports, which show a nearly linear relationship between refractive index and photon energy in the temperature range of −20–120 °C, an abnormal drop has been observed in the refractive index spectrum at the wavelengths near the absorption threshold. To theoretically understand this anomalous dispersion, we first bring the HigherCPs model and M0CP model together to provide a good description of inter-band transition and rewrite the dielectric function of Ge near its absorption edge. Then, the abnormal drop is well interpreted by introducing the Wannier exciton model to the combined model. Furthermore, we evaluate the band gap E0 and Lorentzian broadening of the exciton line as the function of temperature with this new model. The experimental and theoretical results allow for the optimized design of the Ge-based optical applications near the C-band of optical fiber communication.