Exciton Ground Research Articles

Upconversion electroluminescence in 2D semiconductors integrated with plasmonic tunnel junctions.

Plasmonic tunnel junctions are a unique electroluminescent system in which light emission occurs via an interplay between tunnelling electrons and plasmonic fields instead of electron-hole recombination as in conventional light-emitting diodes. It was previously shown that placing luminescent molecules in the tunneling pathway of nanoscopic tunnel junctions results in peculiar upconversion electroluminescence where the energy of emitted photons exceeds that of excitation electrons. Here we report the observation of upconversion electroluminescence in macroscopic van der Waals plasmonic tunnel junctions comprising gold and few-layer graphene electrodes separated by a ~2-nm-thick hexagonal boron nitride tunnel barrier and a monolayer semiconductor. We find that the semiconductor ground exciton emission is triggered at excitation electron energies lower than the semiconductor optical gap. Interestingly, this upconversion is reached in devices operating at a low conductance (<10-6 S) and low power density regime (<102 W cm-2), defying explanation through existing proposed mechanisms. By examining the scaling relationship between plasmonic and excitonic emission intensities, we elucidate the role of inelastic electron tunnelling dipoles that induce optically forbidden transitions in the few-layer graphene electrode and ultrafast hot carrier transfer across the van der Waals interface.

Temperature-Dependent Exciton Dynamics in a Single GaAs Quantum Ring and a Quantum Dot.

Micro-photoluminescence was observed while increasing the excitation power in a single GaAs quantum ring (QR) at 4 K. Fine structures at the energy levels of the ground (N = 1) and excited (N = 2) state excitons exhibited a blue shift when excitation power increased. The excited state exciton had a strong polarization dependence that stemmed from the asymmetric localized state. According to temperature-dependence measurements, strong exciton–phonon interaction (48 meV) was observed from an excited exciton state in comparison with the weak exciton–phonon interaction (27 meV) from the ground exciton state, resulting from enhanced confinement in the excited exciton state. In addition, higher activation energy (by 20 meV) was observed for the confined electrons in a single GaAs QR, where the confinement effect was enhanced by the asymmetric ring structure.

Photophysical properties of zero-dimensional perovskites studied by PBE0 and GW+BSE methods

Due to the exceptional photophysical properties and great potential applications in solid state lighting, zero-dimensional halide perovskites with broadband emitting have recently attracted much attention. In this work, to reveal the origin of the broadband absorption and emission spectra of 0D (C4N2H14Br)4SnBrxI6−x (x=3), the ground state and exciton dynamics properties have been studied by hybrid PBE0 functional and the GW+BSE method. Different self-trapped excitons (STEs) are obtained, and their emission energies by PBE0 are consistent well with experimental data. By considering the vibrational broadening of emission, our calculated full width at half maximum of emission accords well with the experiment. The absorption of free exciton and STEs is also calculated by considering the quasiparticle and excitonic effect. Our results show that these light-induced trapped states can be observed by experiments, as confirmed in other similar systems by the femtosecond transient absorption spectra.

Exciton-polaron Rydberg states in monolayer MoSe2 and WSe2

Exciton polaron is a hypothetical many-body quasiparticle that involves an exciton dressed with a polarized electron-hole cloud in the Fermi sea. It has been evoked to explain the excitonic spectra of charged monolayer transition metal dichalcogenides, but the studies were limited to the ground state. Here we measure the reflection and photoluminescence of monolayer MoSe2 and WSe2 gating devices encapsulated by boron nitride. We observe gate-tunable exciton polarons associated with the 1 s–3 s exciton Rydberg states. The ground and excited exciton polarons exhibit comparable energy redshift (15~30 meV) from their respective bare excitons. The robust excited states contradict the trion picture because the trions are expected to dissociate in the excited states. When the Fermi sea expands, we observe increasingly severe suppression and steep energy shift from low to high exciton-polaron Rydberg states. Their gate-dependent energy shifts go beyond the trion description but match our exciton-polaron theory. Our experiment and theory demonstrate the exciton-polaron nature of both the ground and excited excitonic states in charged monolayer MoSe2 and WSe2.

Splitting of the energy spectrum of an indirect exciton upon electron tunnelling between nanoparticles

We report an analytical study of the splitting of the energy spectrum of an electron for a quasi-two-dimensional indirect exciton (Q2D-IX) localised at the ‘dielectric nanoparticle–dielectric medium’ interface. The splitting results from electron tunnelling through a potential barrier separating neighbouring nanoparticles. The obtained expressions determine the energy and spatial parameters of the probability of electron tunnelling and the value of the energy splitting. It is found that tunnelling is possible under rigid conditions for the spatial parameters of the nanosystem and the ratio of the energies of the excited and ground exciton states. Tunnelling-induced splitting of the electron energy can reach 0.1 eV for some dielectric structures. This allows the impact of charge tunnelling on the energy spectrum of Q2D-IX systems to be predicted.

Exciton oscillator strength in two-dimensional Dirac materials

Exciton problem is solved in the two-dimensional Dirac model with allowance for strong electron-hole attraction. The exciton binding energy is assumed smaller than but comparable to the band gap. The exciton wavefunction is found in the momentum space as a superposition of all four two-particle states including electron and hole states with both positive and negative energies. The matrix element of exciton generation is shown to depend on the additional components of the exciton wavefunction. Both the Coulomb and the Rytova-Keldysh potentials are considered. The dependence of the binding energy on the coupling constant is analyzed for the ground and first excited exciton states. The binding energy and the oscillator strength are studied as functions of the environmental-dependent dielectric constant for real transition metal dichalcogenide monolayers. We demonstrate that the multicomponent nature of the exciton wavefunction is crucial for description of resonant optical properties of two-dimensional Dirac systems.

Excitonic Energy Transfer in Heterostructures of Quasi-2D Perovskite and Monolayer WS2.

Quasi-two-dimensional (2D) organic-inorganic hybrid perovskite is a re-emerging material with strongly excitonic absorption and emission properties that are attractive for photonics and optoelectronics. Here we report the experimental observation of excitonic energy transfer (ET) in van der Waals heterostructures consisting of quasi-2D hybrid perovskite (C6H5C2H4NH3)2PbI4 (PEPI) and monolayer WS2. Photoluminescence excitation spectroscopy reveals a distinct ground exciton resonance feature of perovskite, evidencing ET from perovskite to WS2. We find unexpectedly high photoluminescence enhancement factors of up to ∼8, which cannot be explained by single-interface ET. Our analysis reveals that interlayer ET across the bulk of the layered perovskite also contributes to the large enhancement factor. Further, from the weak temperature dependence of the lower-limit ET rate, which we found to be ∼3 ns-1, we conclude that the Förster-type mechanism is responsible.

Accurate modeling of electron-hole binding in CuCl. I. Exciton states

We present an accurate variational approach for calculating the ground and excited exciton states in CuCl, and provide detailed comparison with measured polariton energies of excited exciton states. Computed exciton energies and oscillator strengths allow us to reproduce the polariton dispersion of up to four exciton states with unprecedented accuracy. A reinterpretation of the observed $1s$-exciton binding energy shows that the actual Coulomb energy in the exciton ground state is more than 50% larger than the observed binding energy, with important consequences for calculation of exciton complexes such as the biexciton.

Band nesting and exciton spectrum in monolayer MoS2

We discuss here the effect of band nesting and topology on the spectrum of excitons in a single layer of MoS$_2$, a prototype transition metal dichalcogenide material. We solve for the single particle states using the ab initio based tight-binding model containing metal $d$ and sulfur $p$ orbitals. The metal orbitals contribution evolving from $K$ to $\Gamma$ points results in conduction-valence band nesting and a set of second minima at $Q$ points in the conduction band. There are three $Q$ minima for each $K$ valley. We accurately solve the Bethe-Salpeter equation including both $K$ and $Q$ points and obtain ground and excited exciton states. We determine the effects of the electron-hole single particle energies including band nesting, direct and exchange screened Coulomb electron-hole interactions and resulting topological magnetic moments on the exciton spectrum. The ability to control different contributions combined with accurate calculations of the ground and excited exciton states allows for the determination of the importance of different contributions and a comparison with effective mass and $k\cdot p$ massive Dirac fermion models.

Harnessing Exciton-Exciton Annihilation in Two-Dimensional Semiconductors.

Strong many-body interactions in two-dimensional (2D) semiconductors give rise to efficient exciton-exciton annihilation (EEA). This process is expected to result in the generation of unbound high energy carriers. Here, we report an unconventional photoresponse of van der Waals heterostructure devices resulting from efficient EEA. Our heterostructures, which consist of monolayer transition metal dichalcogenide (TMD), hexagonal boron nitride (hBN), and few-layer graphene, exhibit photocurrent when photoexcited carriers possess sufficient energy to overcome the high energy barrier of hBN. Interestingly, we find that the device exhibits moderate photocurrent quantum efficiency even when the semiconducting TMD layer is excited at its ground exciton resonance despite the high exciton binding energy and large transport barrier. Using ab initio calculations, we show that EEA yields highly energetic electrons and holes with unevenly distributed energies depending on the scattering condition. Our findings highlight the dominant role of EEA in determining the photoresponse of 2D semiconductor optoelectronic devices.

Exciton Fine Structure in Perovskite Nanocrystals.

The bright emission observed in cesium lead halide perovskite nanocrystals (NCs) has recently been explained in terms of a bright exciton ground state [ Becker et al. Nature 2018 , 553 , 189 - 193 ], a claim that would make these materials the first known examples in which the exciton ground state is not an optically forbidden dark exciton. This unprecedented claim has been the subject of intense experimental investigation that has so far failed to detect the dark ground-state exciton. Here, we review the effective-mass/electron-hole exchange theory for the exciton fine structure in cubic and tetragonal CsPbBr3 NCs. In our calculations, the crystal field and the short-range electron-hole exchange constant were calculated using density functional theory together with hybrid functionals and spin-orbit coupling. Corrections associated with long-range exchange and surface image charges were calculated using measured bulk effective mass and dielectric parameters. As expected, within the context of the exchange model, we find an optically inactive ground exciton level. However, in this model, the level order for the optically active excitons in tetragonal CsPbBr3 NCs is opposite to what has been observed experimentally. An alternate explanation for the observed bright exciton level order in CsPbBr3 NCs is offered in terms of the Rashba effect, which supports the existence of a bright ground-state exciton in these NCs. The size dependence of the exciton fine structure calculated for perovskite NCs shows that the bright-dark level inversion caused by the Rashba effect is suppressed by the enhanced electron-hole exchange interaction in small NCs.

The ground exciton state of formamidinium lead bromide perovskite nanocrystals is a singlet dark state.

Lead halide perovskites have emerged as promising new semiconductor materials for high-efficiency photovoltaics, light-emitting applications and quantum optical technologies. Their luminescence properties are governed by the formation and radiative recombination of bound electron-hole pairs known as excitons, whose bright or dark character of the ground state remains unknown and debated. While symmetry analysis predicts a singlet non-emissive ground exciton topped with a bright exciton triplet, it has been predicted that the Rashba effect may reverse the bright and dark level ordering. Here, we provide the direct spectroscopic signature of the dark exciton emission in the low-temperature photoluminescence of single formamidinium lead bromide perovskite nanocrystals under magnetic fields. The dark singlet is located several millielectronvolts below the bright triplet, in fair agreement with an estimation of the long-range electron-hole exchange interaction. Nevertheless, these perovskites display an intense luminescence because of an extremely reduced bright-to-dark phonon-assisted relaxation.

Luminescent Emission of Excited Rydberg Excitons from Monolayer WSe2.

We report the experimental observation of radiative recombination from Rydberg excitons in a two-dimensional semiconductor, monolayer WSe2, encapsulated in hexagonal boron nitride. Excitonic emission up to the 4 s excited state is directly observed in photoluminescence spectroscopy in an out-of-plane magnetic field up to 31 T. We confirm the progressively larger exciton size for higher energy excited states through diamagnetic shift measurements. This also enables us to estimate the 1 s exciton binding energy to be about 170 meV, which is significantly smaller than most previous reports. The Zeeman shift of the 1 s to 3 s states, from both luminescence and absorption measurements, exhibits a monotonic increase of the g-factor, reflecting nontrivial magnetic-dipole-moment differences between ground and excited exciton states. This systematic evolution of magnetic dipole moments is theoretically explained from the spreading of the Rydberg states in momentum space.

Excitonic Effects in Methylammonium Lead Halide Perovskites.

The exciton binding energy in methylammonium lead iodide (MAPbI3) is about 10 meV, around 1/3 of the available thermal energy ( kB T ∼ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination, and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.

Excitonic Properties of Chemically Synthesized 2D Organic-Inorganic Hybrid Perovskite Nanosheets.

2D organic-inorganic hybrid perovskites (OIHPs) represent a unique class of materials with a natural quantum-well structure and quasi-2D electronic properties. Here, a versatile direct solution-based synthesis of mono- and few-layer OIHP nanosheets and a systematic study of their electronic structure as a function of the number of monolayers by photoluminescence and absorption spectroscopy are reported. The monolayers of various OIHPs are found to exhibit high electronic quality as evidenced by high quantum yield and negligible Stokes shift. It is shown that the ground exciton peak blueshifts by ≈40 meV when the layer thickness reduces from bulk to monolayer. It is also shown that the exciton binding energy remains effectively unchanged for (C6 H5 (CH2 )2 NH3 )2 PbI4 with the number of layers. Similar trends are observed for (C4 H9 NH3 )2 PbI4 in contrast to the previous report. Further, the photoluminescence lifetime is found to decrease with the number of monolayers, indicating the dominant role of surface trap states in nonradiative recombination of the electron-hole pairs.

Resonance energy transfer in a dense array of II–VI quantum dots

Forster resonance energy transfer in inhomogeneous dense arrays of epitaxial CdSe/ZnSe quantum dots is demonstrated by time- and space-resolved photoluminescence spectroscopy. The specific feature of this process is the dipole–dipole interaction between the ground exciton levels of small quantum dots and the excited levels of large dots. This interaction brings efficient energy collection and spectral selection of a limited number of emitters. Results of theoretical modeling of optical transitions in spheroidal quantum dots with a Gaussian potential profile agree with the observed features of optical spectra induced by the change of the dominant energy transfer mechanism.

Binding energy of excitons formed from spatially separated electrons and holes in insulating quantum dots

It is found that the binding energy of the ground state of an exciton formed from an electron and a hole spatially separated from each other (the hole is moving within a quantum dot, and the electron is localized above the spherical (quantum dot)–(insulating matrix) interface) in a nanosystem containing insulating Al2O3 quantum dots is substantially increased (by nearly two orders of magnitude) compared to the exciton binding energy in an Al2O3 single crystal. It is established that, in the band gap of an Al2O3 nanoparticle, a band of exciton states (formed from spatially separated electrons and holes) appears. It is shown that there exists the possibility of experimentally detecting the ground and excited exciton states in the band gap of Al2O3 nanoparticles at room temperature from the absorption spectrum of the nanosystem.

Influence of Effects of Self-Polarization and Exciton-Phonon Interactions on the Exciton Energy in Lead Iodide Nanofilms

UDC 538.915; 538.975 In the approximation of effective masses for electronic and phononic – dielectric continuum – systems, the influence of spatial bounding, self-polarization, and exciton-phonon interactions on the exciton state in a flat double nanoheterostructure (a nanofilm) – lead iodide in a polymer matrix –is theoretically investigated for the model of a single infinitely deep quantum well. It is demonstrated that the dominating factor determining the energy of the bottom of the ground exciton band and its binding energy is spatial bounding. The relationship between two other effects depends on the nanofilm thickness, namely, the influence of the self-polarization effect in ultrathin films significantly exceeds that of exciton-phonon interaction.

Enhanced photoresponsive mobility of rubrene nanosheet-based organic field effect transistors through hybridization with CdSe/ZnS quantum dots

Organic field effect transistors (OFETs) were fabricated using a p-type rubrene single nanosheet (NS) as an active layer hybridized with n-type CdSe/ZnS quantum dots (QDs). The dark and photoresponsive (λex=455nm) electrical characteristics of the rubrene NS-based OFETs were investigated with and without the QDs. In dark conditions, the source-drain current (IDS) of the OFETs increased and the threshold voltage was shifted to a positive direction after the partial attachment of the QDs to the surface of the NS. We also observed that the laser confocal microscope (LCM) PL intensity of the rubrene NS decreased through the attachment of the QDs, due to the charge transfer effect. With light irradiation, the photoresponsive IDS and mobility of the OFETs were considerably enhanced by the hybridization with QDs. The results originated from both the ground charge transfer and exciton dissociation effects at the interface of p-type rubrene and n-type QDs heterojunctions.

Polarization selection rules in exciton-based terahertz lasers

Optical pumping of excited exciton states in semiconductor quantum wells is a tool for the realization of ultracompact terahertz (THz) lasers based on stimulated optical transition between excited ($2p$) and ground ($1s$) exciton states. We show that the probability of two-photon absorption by a $2p$ exciton is strongly dependent on the polarization of both photons. Variation of the threshold power for THz lasing by a factor of 5 is predicted by switching from linear to circular pumping. We calculate the polarization dependence of the THz emission and identify photon polarization configurations for achieving maximum THz photon generation quantum efficiency.