Excitons In Quantum Research Articles

Phonon-induced exciton weak localization in two-dimensional semiconductors

We theoretically study the contribution of quantum effects to the exciton diffusion coefficient in atomically thin crystals. It is related to the weak localization caused by the interference of excitonic wavefunctions on the trajectories with closed loops. Due to the weak inelasticity of the exciton–phonon interaction, the effect is present even if the excitons are scattered by long-wavelength acoustic phonons. We consider exciton interaction with longitudinal acoustic phonons with linear dispersion and flexural phonons with quadratic dispersion. We identify the regimes where the weak localization effect can be particularly pronounced. We also briefly address the role of free charge carriers in the exciton quantum transport and, within the self-consistent theory of localization, the weak localization effects beyond the lowest order.

Excitonic resonances control the temporal dynamics of nonlinear optical wave mixing in monolayer semiconductors

Monolayer semiconductors are an emerging platform for strong nonlinear light–matter interactions that are enhanced by the giant oscillator strength of tightly bound excitons. Little attention has been paid to the impact of excitonic resonances on the temporal dynamics of such nonlinearities, since harmonic generation and optical wave mixing are generally considered instantaneous processes. We find that a significant time difference, ranging from −40 to +120 fs, is necessary between two light pulses for optimal sum-frequency generation (SFG) and four-wave mixing (FWM) to occur from monolayer WSe2 when one of the pulses is in resonance with an excitonic transition. These resonances involve both band-edge A excitons and high-lying excitons that comprise electrons from conduction bands far above the bandgap. Numerical simulations in the density-matrix formalism rationalize the distinct dynamics of SFG and FWM. The interpulse delays for maximal SFG and FWM are governed primarily by the lifetime of the one-photon and two-photon resonant states, respectively. The method therefore offers an unconventional probe of the dynamics of excitonic states accessible with either one-photon or two-photon transitions. Remarkably, the longest delay times occur at the lowest excitation powers, indicating a strong nonlinearity that offers exploration potential for excitonic quantum nonlinear optics. Researchers show that resonant coupling of light pulses with excitonic transitions affects the optimal time difference between pulses for sum-frequency generation and four-wave mixing in monolayer WSe2.

(Invited, Digital Presentation) Photocurrent Detection of Cooperative Exciton Quantum Interference in Nanocrystal Thin Films

Colloidal semiconductor quantum dots (QDs) are excellent materials for studying the photophysics of exciton complexes such as biexcitons, triexcitons, and charged excitons (trions). Dynamics of exciton complexes usually determines the performance of optoelectronic devices [1]. For example, trions reduce the optical gain threshold in QD lasers and multiexcitons increase photon-to-current conversion efficiencies via carrier multiplication processes in QD solar cells. In addition, unconventional properties of multiexcitons emerge in coherent processes in QD systems. We recently discovered the high-frequency coherent oscillations with integer multiples of the exciton resonance frequency, which is called multiexciton harmonic quantum coherence [2,3]. The multiexciton coherent properties have been investigated using optical methods. However, to clarify their roles in optoelectronic devices, it is necessary to conduct the electrical detection of multiexciton coherence.Here, we performed photocurrent detection of exciton quantum interference signals in QD thin films. The samples used in this study were closely packed PbS QD thin films. The QD films were sandwiched between the electron and hole transport layers to extract photogenerated carriers. Multiexcitons were generated by phase-locked femtosecond laser pulses, and then their photocurrent quantum interference signals were measured by using a quantum interference technique [4]. The photocurrent interference signal in the weak excitation shows a single sinusoidal oscillation originating from single excitons, while the interference signal changes to the profile involving multiple sinusoidal oscillations with increasing excitation intensity. This means that the multiexciton quantum coherence exhibiting harmonic oscillations is successfully detected in a photocurrent technique [5]. Furthermore, the amplitudes of harmonic quantum coherent signals in coupled QDs are significantly larger than those in isolated QDs. We clarified that the enhancement of the amplitudes is caused by cooperative processes in coupled QDs, where excitons in adjacent QDs interact with each other through their inter-QD coherent coupling. This cooperative effect can provide a new way to use inter-QD coherent coupling in advanced optoelectronic applications, e.g., amplifiers of coherent signals.Part of this work was supported by JSPS KAKENHI (JP19H05465 and JP22H01990) and JST CREST (JPMJCR21B4).

Multifunctional NdBr3 Modifier Enables Remarkable Enhancement in the Performance of Perovskite Light-Emitting Diodes

Quasi-two-dimensional (quasi-2D) perov- skites possess the preponderances of large exciton binding energy and quantum confinement effects compared with three-dimensional (3D) perovskites. The unique properties of quasi-2D perovskite have attracted extensive attention in the field of optoelectronic devices, especially in the light emitting diode (LED) direction. However, the adverse effects between the perovskite emission layer and the popularly used hole transport layer (HTL) Poly(3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) have degrade the device performance, such as large energy level barrier and exciton quenching. Here we demonstrated high performance of LED with enhanced brightness and efficiency by modifying the PEDOT:PSS with NdBr3, which not only decreases exciton quenching, but also decreases HOMO level of the PEDOT:PSS, thereby improving the charge balance. The final performance of the perovskite light-emitting diode (PeLED) device was obtained with a maximum luminance of 18684 cd m−2, a maximum current efficiency (CE) of 48.4 cd A−1 and an external quantum efficiency (EQE) of up to 15.5% when using NdBr3 modified PEDOT:PSS.

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.

Two-Photon Lasing from Two-Dimensional Homologous Ruddlesden-Popper Perovskite with Giant Nonlinear Absorption and Natural Microcavities.

Two-dimensional Ruddlesden-Popper perovskites (RPPs) with multiple quantum well-like structures, strong excitonic quantum confinement, and high stability are promising optical gain media. However, the lasing from such material with a small number of inorganic well layers is difficult to achieve. Herein, we demonstrate the low-threshold upconversion lasing from the homologous RPP (PEA)2(MA)n-1PbnI3n+1 (n = 2 and 3) microflakes with wavelength varies from 598 to 637 nm under 800 nm laser excitation at low temperature (≤153 K). Using the micro Z-scan technique, we discovered that the RPP flakes have a giant two-photon absorption coefficient β as high as 3.6 × 103 cm GW-1, resulting in the effective upconversion transition under two-photon excitation. Furthermore, the self-formation of Fabry-Pérot microcavities provides the support for lasing emission from the n ≥ 2 RPP flakes. Calculation results and microscopic transient absorption measurements reveal that low-threshold lasing is due to the high differential gain coefficient and the suppressed nonradiative Auger recombination rate inside the quantum confinement structures. These properties enable RPPs as potential gain media for developing upconversion microcavity lasers.

Mie Exciton-Polariton in a Perovskite Metasurface

Exciton-polariton arising from strong light-matter interaction between exciton and optical cavity has attracted considerable attention due to its potential applications in Bose-Einstein condensation, low-threshold lasing, and slow light. In recent years, two-dimensional lead halide perovskite has emerged as an ideal candidate for realizing exciton polariton at room temperature because it has large exciton binding energy and quantum yield. Here, we demonstrate that strong coupling could be enabled with a perovskite metasurface that supports multipolar Mie resonance, including magnetic quadrupole dominant, anapole, and toroidal resonances. For an array of perovskite nanodisks, the strong coupling behavior between these resonances and exciton is confirmed by the anticrossing features in absorption spectra mapping, while the Rabi splitting is increased from 230.7 meV in magnetic quadrupole-exciton strong coupling to 253 meV in both anapole-exciton and toroidal-exciton strong coupling. The enhanced Rabi splitting is attributed to the stronger field localization within the perovskite instead of within the air gap. In addition, we find that the Rabi splitting depends on the oscillatory strength of the exciton mode and can then be boosted to 362 meV in anapole-exciton strong coupling. Our results provide promising ways to improve the performance of optoelectronic devices such as low-threshold lasers and slow-light devices.

Entangled Biphoton Enhanced Double Quantum Coherence Signal as a Probe for Cavity Polariton Correlations in Presence of Phonon Induced Dephasing

We theoretically propose a biphoton entanglement-enhanced multidimensional spectroscopic technique as a probe for the dissipative polariton dynamics in the ultrafast regime. It is applied to the cavity-confined monomeric photosynthetic complex that represents a prototypical multi-site excitonic quantum aggregate. The proposed technique is shown to be particularly sensitive to inter-manifold polariton coherence between the two and one-excitation subspaces. It is demonstrated to be able to monitor the dynamical role of cavity-mediated excitonic correlations, and dephasing in the presence of phonon-induced dissipation. The non-classicality of the entangled biphoton sources is shown to enhance the ultra-fast and broadband correlation features of the signal, giving an indication about the underlying state correlations responsible for long-range cavity-assisted exciton migration.

Effect of Crystallinity on Endoergic Singlet Fission in Perylenediimide Single Crystals and Polycrystalline Films

The triplet state energy of bis(3′-aminopentyl)-perylene-(3,4:9,10)-bis(dicarboximide) (C5PDI) in the solid state is 1.1 eV, so that achieving singlet fission (SF) in crystalline films of C5PDI can provide a potential means of delivering triplet excitons to silicon-based solar cells, whose band gap is also 1.1 eV, to enhance their performance by utilizing blue light in the solar spectrum. Here, we use transient absorption spectroscopy and microscopy to assess the effect of solid-state order on SF dynamics by comparing C5PDI single crystals and thin polycrystalline films. The X-ray single-crystal structure of C5PDI shows that it forms π-stacked dimers, wherein the PDIs are twisted ∼51° relative to one another. Formation of the correlated triplet pair state 1(T1T1) in the C5PDI single crystals occurs in τ = 56 ± 4 ps mediated by a mixed state having both excited singlet and charge-transfer character, while in a solvent-vapor-annealed C5PDI polycrystalline thin film, 1(T1T1) formation occurs in τ = 169 ± 6 ps. The quantum yield of the 1(T1T1) state formation in each case is nearly unified, yet the free triplet exciton quantum yield in the single crystals is 70%, while that in the annealed polycrystalline film is only 29%. Steady-state and time-resolved photoluminescence measurements indicate that the disorder in the polycrystalline film hinders free triplet excitons via long-lived excimer trap states at sites with suboptimal electronic coupling. The higher free triplet yield in the single crystal also clearly shows that the high degree of molecular order in the crystal enables competition between triplet annihilation and diffusional escape, which is critical for utilizing the triplet excitons to enhance solar cell performance.

Excitonic insulators and Gross-Neveu models

We introduce a generalized Gross-Neveu (GN) model to describe the excitonic instabilities in two different systems: a small overlap semi-metal (SM) and a small gap semi-conductor (SMC), both in two (2d) and three-dimensions (3d). We identify the excitonic order parameter (EOP) and obtain the effective potential within the Large $N$ limit approach where the GN model can be exactly solved. We obtain the excitonic insulator (EI) phase diagrams as a function of temperature, chemical potential, overlap between bands and gaps of the system. We show that the EI may undergo first- or second-order thermal transitions depending on the regime whereupon this phase is approached. We also investigate the expected thermodynamic signatures for the specific heat above the fine-tuned excitonic quantum critical point (EQCP), in both 2d and 3d, in the SMC regime. We show that the EQCP is a different kind of critical point since although the EOP vanishes at the EQCP, there is always a finite gap in the SMC regime. We find that for high temperatures, the specific heat might exhibit a scaling behavior in the form $C_V/T \propto T^{(d-z)/z}$, where $d$ is the dimension of the system and $z$ is the dynamical critical exponent. The very low temperature behavior has a dominant exponential thermally activated term due to the presence of a gap that does not vanish at the excitonic transition.

Observation of moiré excitons in the twisted WS2/WS2 homostructure.

Moiré superlattices offer a fascinating platform for designing the properties of optical excitons. The moiré pattern can generate an ordered exciton array in space, making it possible for topological excitons and quantum emitters. Recently, evidence of moiré excitons in the twisted heterostructures of TMDs has been widely reported. However, to date, the capture and investigation of moiré excitons in the twisted homostructure (T-HS) remain elusive. Here, we report the observation of moiré excitons in the WS2/WS2 T-HS with a twist angle of about 1.5°. The PL spectrum of the T-HS region shows many small peaks with nearly constant peak spacing, which is attributed to the reconstructed moiré potential generated by the reconstructed moiré pattern to confine the intralayer excitons, thereby forming an ordered moiré exciton array. Furthermore, we have studied the influence of temperature and laser power on the moiré excitons as well as the valley polarization of the moiré excitons. Our results provide a promising prospect for further exploration of artificial excitonic crystals and quantum emitters of TMD moiré patterns.

Квантовые биения экситонов с легкими и тяжелыми дырками в спектрах отражения в квантовой яме GaAs/AlGaAs

In this work we experimentally study dynamics of states of light- and heavy-hole excitons in a quantum well under coherent excitation of both excitonic resonances using co- and cross- linear and circular polarizations of pump and probe beams. In the parameters of excitonic resonances quantum beats are observed. Their polarization-dependent existence is used to determine the structure of states of the light- and heavy-hole exciton system by means of theoretical modelling of experimental data.

Towards high-temperature electron-hole condensate phases in monolayer tetrels metal halides: Ultra-long excitonic lifetimes, phase diagram and exciton dynamics

Excitons as composite bosons have been predicted to condense into Bose Einstein Condensation (BEC), Berezinskii-Kosterlitz-Thouless (BKT) superfluid or electron-hole liquid (EHL) states. However, short lifetime and small binding energy are the main obstacles that hinder the formation and observation of excitonic condensate at high temperature. Here we demonstrate excellent two-dimensional Tetrel Metal Halides (TMHs) platforms for excitonic quantum phase transition researches. We find that excitons in those monolayers possess effective masses similar to the free electron, promising large thermal de Broglie wavelengths. They can maintain stable bosonic characteristic at high temperature and concentration up to 1012 cm−2. The calculation on PbI2, PbBr2, PbCl2, SnI2, SnBr2, SnCl2 indicates BEC transition temperatures at 49 K, 103 K, 252 K, 36 K, 78 K, 152 K, comparable to the experimentally observed exciton BEC in MoSe2–WSe2 bilayer and 1 T-TiSe2 at 100 K and 190 K respectively. Besides, we confirm that the thermal equilibrium of excitonic subsystem can be established really fast, up to ∼10–100 fs. The excitons can live for ∼1–100 μs without direct radiation, beneficial for the formation and observation of condensate state. Our result paves the way not only for studies of quantum phase transition researches, but also for high-temperature excitonic devices.

Failed excitonic quantum phase transition in Ta2Ni(Se1−xSx)5

We study the electronic phase diagram of the excitonic insulator candidates Ta$_2$Ni(Se$_{1-x}$S$_x$)$_5$ [x=0, ... ,1] using Raman spectroscopy. Critical excitonic fluctuations are observed, that diminish with $x$ and ultimately shift to high energies, characteristic of a quantum phase transition. Nonetheless, a symmetry-breaking transition at finite temperatures is detected for all $x$, exposing a cooperating lattice instability that takes over for large $x$. Our study reveals a failed excitonic quantum phase transition, masked by a preemptive structural order.

Quasi-1D exciton channels in strain-engineered 2D materials.

Strain engineering is a powerful tool in designing artificial platforms for high-temperature excitonic quantum devices. Combining strong light-matter interaction with robust and mobile exciton quasiparticles, two-dimensional transition metal dichalcogenides (2D TMDCs) hold great promise in this endeavor. However, realizing complex excitonic architectures based on strain-induced electronic potentials alone has proven to be exceptionally difficult so far. Here, we demonstrate deterministic strain engineering of both single-particle electronic bandstructure and excitonic many-particle interactions. We create quasi-1D transport channels to confine excitons and simultaneously enhance their mobility through locally suppressed exciton-phonon scattering. Using ultrafast, all-optical injection and time-resolved readout, we realize highly directional exciton flow with up to 100% anisotropy both at cryogenic and room temperatures. The demonstrated fundamental modification of the exciton transport properties in a deterministically strained 2D material with effectively tunable dimensionality has broad implications for both basic solid-state science and emerging technologies.

Phonon-Assisted Intervalley Scattering Determines Ultrafast Exciton Dynamics in MoSe_{2} Bilayers.

While valleys (energy extrema) are present in all band structures of solids, their preeminent role in determining exciton resonances and dynamics in atomically thin transition metal dichalcogenides (TMDC) is unique. Using two-dimensional coherent electronic spectroscopy, we find that exciton decoherence occurs on a much faster timescale in MoSe_{2} bilayers than that in the monolayers. We further identify two population relaxation channels in the bilayer, a coherent and an incoherent one. Our microscopic model reveals that phonon-emission processes facilitate scattering events from the K valley to other lower-energy Γ and Λ valleys in the bilayer. Our combined experimental and theoretical studies unequivocally establish different microscopic mechanisms that determine exciton quantum dynamics in TMDC monolayers and bilayers. Understanding exciton quantum dynamics provides critical guidance to the manipulation of spin-valley degrees of freedom in TMDC bilayers.

Highly Efficient Quasi-2D Perovskite Light-Emitting Diodes Incorporating a TADF Dendrimer as an Exciton-Retrieving Additive.

Although small organics or polymer additives have been introduced to enhance film formation and radiative recombination of perovskite light-emitting diodes (PeLEDs), the exciton utilization and quantum efficiency need further optimization. Here, we introduce a thermal-activated delayed fluorescence (TADF) dendrimer as an additive to enhance the surface coverage and reduce the trap state of the grain boundary. More importantly, the TADF nature of such an additive can retrieve the exciton dissociated from perovskite or trapped by the grain boundary and then transfer the energy back to emissive perovskite through the Förster energy transfer process. Since the triplets can be reused by reverse intersystem crossing in such a TADF additive, the theoretical exciton utilization is 100%. As a result, the optimized PeLEDs cooperating with a TADF additive achieved a high current efficiency of 39.0 cd A-1 and an ultrabright luminescence of 18,000 cd m-2, which are almost 5 times higher than those of the control device without an additive. Moreover, the device stability monitored by half-lifetime at 1000 cd m-2 enhanced 2 times after introducing the TADF dendrimer as an additive. The parent dendrimer without a TADF feature was also synthesized as an additive to explore the mechanism action, which found that 54% enhancement of device efficiency can be attributed to defect passivating, while 46% was assigned to retrieved energy. This research first demonstrates that the TADF dendrimer is a promising exciton-retrieving additive for enhancing the performance of PeLEDs by passivating defect, filling up grain boundary, and retrieving leakage exciton.

Promoting Energy Transfer via Manipulation of Crystallization Kinetics of Quasi-2D Perovskites for Efficient Green Light-Emitting Diodes.

Quasi-2D (Q-2D) perovskites are promising materials applied in light-emitting diodes (LEDs) due to their high exciton binding energy and quantum confinement effects. However, Q-2D perovskites feature a multiphase structure with abundant grain boundaries and interfaces, leading to nonradiative loss during the energy-transfer process. Here, a more efficient energy transfer in Q-2D perovskites is achieved by manipulating the crystallization kinetics of different-n phases. A series of alkali-metal bromides is utilized to manipulate the nucleation and growth of Q-2D perovskites, which is likely associated with the Coulomb interaction between alkali-metal ions and the negatively charged PbBr6 4- frames. The incorporation of K+ is found to restrict the nucleation of high-n phases and allows the subsequent growth of low-n phases, contributing to a spatially more homogeneous distribution of different-n phases and promoted energy transfer. As a result, highly efficient green Q-2D perovskites LEDs with a champion EQE of 18.15% and a maximum brightness of 25 800cd m-2 are achieved. The findings affirm a novel method to optimize the performance of Q-2D perovskite LEDs.

Signatures of moiré trions in WSe2/MoSe2 heterobilayers.

Moiré superlattices formed by van der Waals materials can support a wide range of electronic phases, including Mott insulators1-4, superconductors5-10 and generalized Wigner crystals2. When excitons are confined by a moiré superlattice, a new class of exciton emerges, which holds promise for realizing artificial excitonic crystals and quantum optical effects11-16. When such moiré excitons are coupled to charge carriers, correlated states may arise. However, no experimental evidence exists for charge-coupled moiré exciton states, nor have their properties been predicted by theory. Here we report the optical signatures of trions coupled to the moiré potential in tungsten diselenide/molybdenum diselenide heterobilayers. The moiré trions show multiple sharp emission lines with a complex charge-density dependence, in stark contrast to the behaviour of conventional trions. We infer distinct contributions to the trion emission from radiative decay in which the remaining carrier resides in different moiré minibands. Variation of the trion features is observed in different devices and sample areas, indicating high sensitivity to sample inhomogeneity and variability. The observation of these trion features motivates further theoretical and experimental studies of higher-order electron correlation effects in moiré superlattices.

(Invited) Toward Spectral Homogeneity in Guanine Functionalized SWCNTs

Different chiralities of single-walled carbon nanotubes (SWCNTs) have distinct electronic and optical properties, with a range of band gaps that make them appropriate for several opto-electronic applications. Due to the unusually high mobility of charge carriers in SWCNTs,1 semiconducting SWCNTs may find use as logic gates in future high-speed nano-electronic circuits. With this in mind, controlled modulation of the optical and electronic properties of individual carbon nanotubes may be valuable in optoelectronic and nano-bioelectronic applications.It was recently discovered that when SWCNTs coated with single-stranded DNA are exposed to singlet oxygen, the guanine nucleobases in the DNA coatings form covalent bonds to the nanotube sidewalls.2 This alters the nanotube electronic and optical properties, allowing spatial and energetic control through selection of the DNA base sequence. However, the functionalized products display undesired spectral broadening interpreted as excess inhomogeneity compared to the pristine SWCNT reactants.Here we will present the results of efforts to understand and reduce this inhomogeneity. Our study has used molecular dynamics simulations of ssDNA – SWCNT hybrid structures, as well as analysis of experimental data. We have explored the effects of varied reaction conditions, including temperature, ionic strength, and pH on product yields and spectra. An unexpected inverse dependence of functionalization density on reaction temperature was uncovered. We will also present photophysical results extracted from spectral data via statistical modeling, including the energy depth of localized exciton quantum wells created by functionalization. The analysis points to fluorescence red shifts that reflect the random number of functionalization sites felt by excitons. Dürkop, T.; Getty, S. A.; Cobas, E.; Fuhrer, M. S. Extraordinary Mobility in Semiconducting Carbon Nanotubes. Nano Lett. 2004, 4, 35-39.Zheng, Y.; Bachilo, S. M.; Weisman, R. B. Controlled Patterning of Carbon Nanotube Energy Levels by Covalent DNA Functionalization. ACS Nano 2019, 13, 8222-8228.