Single-exciton States Research Articles

Efficient and stable green organic light-emitting diode utilizing an asymmetric butterfly-shaped chromophore with enhanced reverse intersystem crossing and suppressed exciton annihilation

Intermolecular electron-exchange interactions involving long-lived triplet state excitons dominate the quenching process of the films. In this work, a butterfly-shaped thermally activated delayed fluorescence (TADF) emitter 10,10′-(5-((3,5-di(9H-carbazol-9-yl)phenyl)sulfonyl)-1,3-phenylene)bis(9,9-dimethyl-9,10-dihydroacridine) (BCZ-DPS-BAD) with diphenylsulfone skeleton is constructed by modulating the rigid steric hindrance on the electron donor fragment to weaken intermolecular electron-exchange interactions. Analysis of the ground and excited state properties, crystal structure, steady-state and transient photophysical characteristics reveals that BCZ-DPS-BAD exhibits loose intermolecular arrangements with no direct facing close packing and weak π–π interactions of 4.18 Å and 4.67 Å. The triplet state excitons can swiftly return to the single exciton state in accordance with a short delayed fluorescence lifetime (2.3 μs) and a quick reverse intersystem crossing rate (1.85 × 106 s−1), obstructing the way for the triplet state to lose energy. A remarkable maximum external quantum efficiency of 21.8 %, maximum current efficiency of 56.8 cd/A and exciton utilization rate of 82 % is achieved for BCZ-DPS-BAD-based green non-doped OLED, concomitant with Commission Internationale d'Eclairage (CIE) coordinates of (0.30, 0.50). Notably, BCZ-DPS-BAD behaves stable non-doped OLED performance with efficiency roll-off of 4 % at 1000 cd m−2.

Biexciton Blinking in CdSe-Based Quantum Dots.

Experiments on single colloidal quantum dots (QDs) have revealed temporal fluctuations in the emission efficiency of the single-exciton state. These fluctuations, often termed "blinking", are caused by opening/closing of charge-carrier traps and/or charging/discharging of the QD. In the regime of strong optical excitation, multiexciton states are formed. The emission efficiencies of multiexcitons are lower because of Auger processes, but a quantitative characterization is challenging. Here, we quantify fluctuations of the biexciton efficiency for single CdSe/CdS/ZnS core-shell QDs. We find that the biexciton efficiency "blinks" significantly. The additional electron due to charging of a QD accelerates Auger recombination by a factor of 2 compared to the neutral biexciton, while opening/closing of a charge-carrier trap leads to an increase of the nonradiative recombination rate by a factor of 4. To understand the fast rate of trap-assisted recombination, we propose a revised model for trap-assisted recombination based on reversible trapping. Finally, we discuss the implications of biexciton blinking for lasing applications.

Dynamics of an excitation-transfer trimer: Interference, coherence, Berry's phase development, and vibrational control of non-adiabaticity.

We detail several interesting features in the dynamics of an equilaterally shaped electronic excitation-transfer (EET) trimer with distance-dependent intermonomer excitation-transfer couplings. In the absence of electronic-vibrational coupling, symmetric and antisymmetric superpositions of two single-monomer excitations are shown to exhibit purely constructive, oscillatory, and purely destructive interference in the EET to the third monomer, respectively. In the former case, the transfer is modulated by motion in the symmetrical framework-expansion vibration induced by the Franck-Condon excitation. Distortions in the shape of the triangular framework degrade that coherent EET while activating excitation transfer in the latter case of an antisymmetric initial state. In its symmetrical configuration, two of the three single-exciton states of the trimer are degenerate. This degeneracy is broken by the Jahn-Teller-active framework distortions. The calculations illustrate closed, approximately circular pseudo-rotational wave-packet dynamics on both the lower and the upper adiabatic potential energy surfaces of the degenerate manifold, which lead to the acquisition after one cycle of physically meaningful geometric (Berry) phases of π. Another manifestation of Berry-phase development is seen in the evolution of the vibrational probability density of a wave packet on the lower Jahn-Teller adiabatic potential comprising a superposition of clockwise and counterclockwise circular motions. The circular pseudo-rotation on the upper cone is shown to stabilize the adiabatic electronic state against non-adiabatic internal conversion via the conical intersection, a dynamical process analogous to Slonczewski resonance. Strategies for initiating and monitoring these various dynamical processes experimentally using pre-resonant impulsive Raman excitation, short-pulse absorption, and multi-dimensional wave-packet interferometry are outlined in brief.

Degenerate parametric down-conversion facilitated by exciton-plasmon polariton states in a nonlinear plasmonic cavity

We study the effect of degenerate parametric down-conversion (DPDC) in an ensemble of two-level quantum emitters (QEs) coupled via near-field interactions to a single surface plasmon (SP) mode of a nonlinear plasmonic cavity. For this purpose, we develop a quantum driven-dissipative model capturing non-equilibrium dynamics of the system in which incoherently pumped QEs have transition frequency tuned near the second-harmonic response of the SPs. Considering the strong coupling regime, i.e. the SP-QE interaction rate exceeds system dissipation rates, we find a critical SP-QE coupling attributed to the phase transition between normal and lasing steady states. Examining fluctuations above the system’s steady states, we predict new elementary excitations, namely, the exciton-plasmon polaritons formed by the two-SP quanta and single-exciton states of QEs. The contribution of two-SP quanta results in the linear scaling of the SP-QE interaction rate with the number of QEs, , as opposed to the -scaling known for the Dicke and Tavis–Cummings models. We further examine how SP-QE interaction scaling affects the polariton dispersions and power spectra in the vicinity of the critical coupling. For this purpose, we compare the calculation results assuming a finite ensemble of QEs and the model thermodynamic limit. The calculated power spectra predict an interplay of coherent photon emission by QEs near the second-harmonic frequency and correlated photon-pair emission at the fundamental frequency by the SPs (i.e. the photonic DPDC effect).

Coherent excitation energy transfer processes in two-dimensional para-sexiphenyl molecular clusters

Excitation energy transfer is one of the most important factors affecting the applications of para-sexiphenyl devices. The study of exciton dynamics and exciton coherence effect of para-sexiphenyl clusters under external field excitation is important in order to improve the performance of molecular devices composed of para-sexiphenyl and its related derivatives. In this work, the two-dimensional disc-like para-sexiphenyl molecular cluster is used as the object of study. The molecular system is simplified into a two-level model based on its structural features and energy level distribution. Within the framework of density matrix theory, the exciton dynamics and exciton coherence behavior of disk-like para-hexaphene molecular clusters excited by different pulse fields are analyzed through using the mathematical mean value approximation of the operator. The results show that when long pulses are used to excite para-sexiphenyl clusters, the single exciton state characteristic appears and is insensitive to the change of excited external field strength. When the clusters are subjected to strong pulsed fields with short pulse widths, multiple excitons are excited simultaneously in the cluster, forming multiple exciton states, with the exciton energy levels shifting toward lower energy and new hybrid states appearing. In the optical response spectrum, there appear multiple resonance peaks. And as the pulse field is enhanced, the multi-exciton effect becomes apparent and the hybridization energy level increases. Under short pulse excitation, the excited states are distributed differently in different energy regions, but all of them show obvious symmetry. As the highest-energy exciton states of H-type clusters are preferentially excited, we analyze the exciton state population and the exciton coherence evolution with time in the high-energy exciton state. With the pulse field increases, Rabi oscillations appear and the exciton coherence effect increases. When the pulsed field reaches a certain field strength, the exciton oscillation cooperativity disappears in the first 100 fs, showing the non-local characteristic. The position of the wave trough of the exciton state population corresponds to the peak in the exciton coherence size. It indicates that when the pulse field is intense enough, a large number of molecules are in the exciton coherent state during the pulsed excitation, and transient out-of-domain phenomena occur.

Real Space Visualization of Entangled Excitonic States in Charged Molecular Assemblies.

Entanglement of excitons holds great promise for the future of quantum computing, which would use individual molecular dyes as building blocks of their circuitry. Studying entangled excitonic eigenstates emerging in coupled molecular assemblies in the near-field with submolecular resolution has the potential to bring insight into the photophysics of these fascinating quantum phenomena. In contrast to far-field spectroscopies, near-field spectroscopic mapping permits direct identification of the individual eigenmodes, type of exciton coupling, including excited states otherwise inaccessible in the far field (dark states). Here we combine tip-enhanced spectromicroscopy with atomic force microscopy to inspect delocalized single-exciton states of charged molecular assemblies engineered from individual perylenetetracarboxylic dianhydride (PTCDA) molecules. Hyperspectral mapping of the eigenstates and comparison with calculated many-body optical transitions reveals a second low-lying excited state of the anion monomers and its role in the exciton entanglement within the assemblies. We demonstrate control over the exciton coupling by switching the assembly charge states. Our results reveal the possibility of tailoring excitonic properties of organic dye aggregates for advanced functionalities and establish the methodology to address them individually at the nanoscale.

Understanding radiative transitions and relaxation pathways in plexcitons

Summary Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.

How Exciton and Single Carriers Block the Excitonic Transition in Two-Dimensional Cadmium Chalcogenide Nanoplatelets.

Cadmium chalcogenide nanoplatelets (NPLs) possess unique properties and have shown great potential in lasing, light-emitting diodes, and photocatalytic applications. However, the exact natures of the band-edge exciton and single carrier (electron and hole) states remain unclear, even though they affect the key properties and applications of these materials. Herein, we study the contribution of a single carrier (electron or hole) state to phase space filling of single exciton states of cadmium chalcogenide NPLs. With pump fluence dependent TA study and selective electron removal, we determine that a single electron and hole states contribute 85% and 12%, respectively, to the blocking of the excitonic transition in CdSe/ZnS core/shell NPLs. These observations can be rationalized by a model of band-edge exciton and single carrier states of 2D NPLs that differs significantly from that of quantum dots.

Oxygen Stabilizes Photoluminescence of CdSe/CdS Core/Shell Quantum Dots via Deionization

By taking advantage of well-defined spectroscopic signatures of high-quality CdSe/CdS core/shell QDs, the effects of oxygen on photoluminescence (PL) of QDs were studied systematically and quantitatively at both single-dot and ensemble (on substrate and in solution) levels, which reveals a unified yet simple picture. With a sufficient amount of oxygen in the system during photoexcitation, the core/shell QDs in all forms would be deionized timely from the photogenerated and inefficient trion state back to the efficient single-exciton state, with superoxide radicals as the reduction product of oxygen. Under a given excitation power, rates of both spontaneous deionization and photodeionization channels increased by increasing the oxygen pressure, but photoionization of the QDs was barely affected by the oxygen pressure. While stabilizing PL by oxygen was identified for both CdSe plain core and CdSe/CdS core/shell QDs, irreversible photocorrosion was only observed for CdSe plain core QDs, suggesting the importance of high-quality epitaxial shells for QDs in various applications.

Effects of interface-potential smoothness and wavefunction delocalization on Auger recombination in colloidal CdSe-based core/shell quantum dots.

Auger nonradiative recombination dominates decay of multicarrier states in high quality colloidal quantum dots (QDs) and thus is critical for many of their optical and optoelectronic applications. Controlling interface-potential smoothness and wavefunction delocalization are proposed as two main strategies for Auger engineering in core/shell QDs. Here, a series of CdSe-based core/shell QDs with nearly ideal optical quality of their single-exciton states are developed and applied for studying biexciton quantum yields and Auger nonradiative recombination rates. Comparative experiments find that the interface-potential smoothness has little influence on biexciton quantum yield and Auger rates of these core/shell QDs with the same CdS outer shells. In contrast, with a fixed total size of the series of QDs, the decreasing hole wavefunction delocalization can increase the Auger rates of positive trions by ∼400%. A mild decrease in electron wavefunction delocalization among the series of QDs results in a small increase in the Auger rates of negative trions (∼50%). Smoothing the core/shell interface can indeed affect the Auger rates, but this is by the way of altering wavefunction delocalization. These findings highlight the importance of control of wavefunction delocalization among the strategies of Auger engineering and provide guidelines for rational design QDs for applications.

Applications of Huang–Rhys theory in semiconductor optical spectroscopy

A brief review of Huang–Rhys theory and Albrechtos theory is provided, and their connection and applications are discussed. The former is a first order perturbative theory on optical transitions intended for applications such as absorption and emission involving localized defect or impurity centers, emphasizing lattice relaxation or mixing of vibrational states due to electron–phonon coupling. The coupling strength is described by the Huang–Rhys factor. The latter theory is a second order perturbative theory on optical transitions intended for Raman scattering, and can in-principle include electron–phonon coupling in both electronic states and vibrational states. These two theories can potentially be connected through the common effect of lattice relaxation – non-orthonormal vibrational states associated with different electronic states. Because of this perceived connection, the latter theory is often used to explain resonant Raman scattering of LO phonons in bulk semiconductors and further used to describe the size dependence of electron–phonon coupling or Huang–Rhys factor in semiconductor nanostructures. Specifically, the A term in Albrechtos theory is often invoked to describe the multi-LO-phonon resonant Raman peaks in both bulk and nanostructured semiconductors in the literature, due to the misconception that a free-exciton could have a strong lattice relaxation. Without lattice relaxation, the A term will give rise to Rayleigh or elastic scattering. Lattice relaxation is only significant for highly localized defect or impurity states, and should be practically zero for either single particle states or free exciton states in a bulk semiconductor or for confined states in a semiconductor nanostructure that is not extremely small.

Tunneling blockade and single-photon emission in GaAs double quantum wells

We report on the selective excitation of single impurity-bound exciton states in a GaAs double quantum well (DQW). The structure consists of two quantum wells (QWs) coupled by a thin tunnel barrier. The DQW is subject to a transverse electric field to create spatially indirect inter-QW excitons with electrons and holes located in different QWs. We show that the presence of intra-QW charged excitons (trions) blocks carrier tunneling across the barrier to form indirect excitons, thus opening a gap in their emission spectrum. This behavior is attributed to the low binding energy of the trions. Within the tunneling blockade regime, emission becomes dominated by processes involving excitons bound to single shallow impurities, which behave as two-level centers activated by resonant tunneling. The quantum nature of the emission is confirmed by the antibunched photon emission statistics. The narrow distribution of emission energies ($\ensuremath{\sim}10$ meV) and the electrical connection to the QWs make these single-exciton centers interesting candidates for applications in single-photon sources.

Multiexcitons in flexible Rydberg aggregates

Flexible Rydberg aggregates, assemblies of few Rydberg atoms coherently sharing electronic excitations while undergoing directed atomic motion, show great promise as quantum simulation platform for nuclear motional dynamics in molecules or quantum energy transport. Here we study additional features that are enabled by the presence of more than a single electronic excitation, thus considering multi-exciton states. We describe cases where these can be decomposed into underlying single exciton states and then present dynamical scenarios with atomic motion that illustrate exciton-exciton collisions, exciton routing, and strong non-adiabatic effects in simple one-dimensional settings.

Excitons in Single-Walled Carbon Nanotubes and Their Dynamics.

Understanding exciton dynamics in single-walled carbon nanotubes (SWCNTs) is essential to unlocking the many potential applications of these materials. This review summarizes recent progress in understanding exciton photophysics and, in particular, exciton dynamics in SWCNTs. We outline the basic physical and electronic properties of SWCNTs, as well as bright and dark transitions within the framework of a strongly bound one-dimensional excitonic model. We discuss the many facets of ultrafast carrier dynamics in SWCNTs, including both single-exciton states (bright and dark) and multiple-exciton states. Photophysical properties that directly relate to excitons and their dynamics, including exciton diffusion lengths, chemical and structural defects, environmental effects, and photoluminescence photon statistics as observed through photon antibunching measurements, are also discussed. Finally, we identify a few key areas for advancing further research in the field of SWCNT excitons and photonics.

Experimental Verification of the Very Strong Coupling Regime in a GaAs Quantum Well Microcavity.

The dipole coupling strength g between cavity photons and quantum well excitons determines the regime of light matter coupling in quantum well microcavities. In the strong coupling regime, a reversible energy transfer between exciton and cavity photon takes place, which leads to the formation of hybrid polaritonic resonances. If the coupling is further increased, a hybridization of different single exciton states emerges, which is referred to as the very strong coupling regime. In semiconductor quantum wells such a regime is predicted to manifest as a photon-mediated electron-hole coupling leading to different excitonic wave functions for the two polaritonic branches when the ratio of the coupling strength to exciton binding energy g/E_{B} approaches unity. Here, we verify experimentally the existence of this regime in magneto-optical measurements on a microcavity characterized by g/E_{B}≈0.64, showing that the average electron-hole separation of the upper polariton is significantly increased compared to the bare quantum well exciton Bohr radius. This yields a diamagnetic shift around 0 detuning that exceeds the shift of the lower polariton by 1 order of magnitude and the bare quantum well exciton diamagnetic shift by a factor of 2. The lower polariton exhibits a diamagnetic shift smaller than expected from the coupling of a rigid exciton to the cavity mode, which suggests more tightly bound electron-hole pairs than in the bare quantum well.

Scattering amplitudes for dark and bright excitons

Using the composite boson many-body formalism that takes single-exciton states rather than free carrier states as a basis, we derive the integral equation fulfilled by the exciton-exciton effective scattering from which the role of fermion exchanges can be unraveled. For excitons made of -spin electrons and -spin holes, as in GaAs heterostructures, one major result is that most spin configurations lead to brightness-conserving scatterings with equal amplitude Δ, despite differences in the carrier exchanges involved. A brightness-changing channel also exists when two opposite-spin excitons scatter: dark excitons can end either in the same dark states with an amplitude , or in opposite-spin bright states , with a different amplitude , the number of carrier exchanges involved in these scatterings being even or odd, respectively. Another major result is that these amplitudes are linked by a striking relation, , which has decisive consequence on exciton Bose-Einstein condensation. By using Born values, we show that the exciton condensate can be optically observed through a bright part when excitons have large dipole only, that is, when the electrons and holes are in two well-separated layers, as in current experiments.

Multiphoton Emission Enhancement from a Single Colloidal Quantum Dot Using SiO2-Coated Silver Nanoparticles.

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using SiO2-coated silver nanoparticles (Ag/SiO2) as the plasmonic nanostructure. Using Ag/SiO2 with five different SiO2 shell thicknesses, we observed modification of the emission behavior depending on the distance between the NQD and silver nanoparticle (AgNP). The single-photon emission from a single NQD converted to multiphoton emission with a shortening of the emission lifetime as the NQD–AgNP distance decreased, whereas an increase and decrease in the emission intensity were observed. From the distance-dependent results, we concluded that the probability of multiphoton emission was increased by the quenching of the single-exciton state due to energy transfer from the NQD to the AgNP and that the emission intensity was modified by the enhancement of the excitation rate and quenching. These results indicate that the plasmonic nanostructure is very effective in controlling the emission photon statistics, that is, single- and multi-photon emission and the emission intensity from the single NQD, which is difficult to achieve in an NQD alone.

Spectroscopy of optical gain in low threshold colloidal quantum dot laser media: dominance of single-exciton states at room temperature

Experimental studies of amplified spontaneous emission (ASE) and lasing from various colloidal II-VI semiconductor nanocrystals have been used as inputs to several microscopic models for underlying optical gain, usually involving permutations of quantum confined multiple excitonic states. Here we focus on particular types of CdSe/ZnCdS and CdSe/ZnS/ZnCdS colloidal quantum dot (CQD) films and elucidate on the discovery of single-exciton states at the fundamental edge as a dominant mechanism for optical gain at room temperature. Pump-probe spectroscopic techniques enable us to measure the onset of gain at ensemble-average exciton occupancy per CQD, = 0.6 and 0.7 for the two types of CQD films at room temperature. Time-resolved measurements, in turn, show how optical gain persists well into the time regime associated with spontaneous emission (nanoseconds), thus providing direct evidence for how the non-radiative Auger recombination processes (~100 ps) can be thwarted. In addition to benefits of the material assets of densely packed CQD films with high luminescence efficiency (quantum yield ~90%) and nanoparticle monodispersity therein, we propose that access to the single-exciton gain regime at room temperature requires a careful spectral balance between the lowest exciton absorption resonance and its corresponding red-shifted spontaneous emission maximum (“Stokes shift”).

Detailed Observation of Multiphoton Emission Enhancement from a Single Colloidal Quantum Dot Using a Silver-Coated AFM Tip.

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using a silver-coated atomic force microscopy tip (AgTip) as the plasmonic nanostructure. Using the AgTip, which exhibited a well-defined localized surface plasmon (LSP) resonance band, we controlled the spectral overlap and the distance between the single NQD and the AgTip. The emission behavior of the single NQD when approaching the AgTip at the nanometer scale was measured using off-resonance (405 nm) and resonance (465 nm) excitation of the LSP. We directly observed the conversion of the single-photon emission from a single NQD to multiphoton emission with reduction of the emission lifetime at both excitation wavelengths as the NQD-AgTip distance decreased, whereas a decrease and increase in the emission intensity were observed at 405 and 465 nm excitation, respectively. By combining theoretical analysis and the numerical simulation of the AgTip, we deduced that the enhancement of the multiphoton emission was caused by the quenching of the single-exciton state due to the energy transfer from the NQD to the AgTip and that the emission intensity was increased by enhancement of the excitation rate due to the electric field of the LSP on the AgTip. These results provide evidence that the photon statistics and the photon flux from the single NQD can be manipulated by the plasmonic nanostructure through control of the spectral overlap and the distance.

Ultrafast Laser Studies of Two-Photon Excited Fluorescence Intermittency in Single CdSe/ZnS Quantum Dots.

Two-photon fluorescence microscopy of single quantum dots conditions has been reported by several groups, with contrasting observations regarding the kinetics and dynamics of fluorescence intermittency or "blinking". Here, we investigate the power dependence, kinetics, and statistics of two photon-excited fluorescence intermittency from single CdSe/ZnS quantum dots in a solid PMMA film as a function of sub-bandgap laser intensity at 800 nm. Fluorescence intermittency is observed at all excitation powers and a quadratic (n = 1.97(3)) dependence of the shot noise-limited fluorescence intensity on the incident laser power is verified, confirming essentially zero background contribution from one-photon excitation processes. Such analyses permit two photon absorption cross sections for single quantum dots to be extracted quantitatively from the data, which reveal good agreement with those obtained from previous two-photon FCS measurements. Strictly inverse power law-distributed off-state dwell times are observed for all excitation powers, with a mean power law exponent ⟨m(off)⟩ = 1.65(4) in excellent agreement with the behavior observed under one-photon excitation conditions. Finally, a superquadratic (n = 2.3(2)) rather than quartic (n = 4) power dependence is observed for the on-state blinking dwell times, which we kinetically analyze and interpret in terms of a novel 2 + 1 "hot" exciton ionization/blinking mechanism due to partially saturated 1-photon sub-bandgap excitation out of the two-photon single exciton state. The kinetic results are consistent with quantum dot photoionization quantum yields from "hot" exciton states (4(1) × 10(-6)) comparable with experimental estimates (10(-6)-10(-5)) of Auger ionization efficiencies out of the biexcitonic state.