Photoexcited Excitons Research Articles

Exciton-Phonon Coupling Induces a New Pathway for Ultrafast Intralayer-to-Interlayer Exciton Transition and Interlayer Charge Transfer in WS2-MoS2 Heterostructure: A First-Principles Study.

Despite the weak, van der Waals interlayer coupling, photoinduced charge transfer vertically across atomically thin interfaces can occur within surprisingly fast, sub-50 fs time scales. An early theoretical understanding of charge transfer is based on a noninteracting picture, neglecting excitonic effects that dominate optical properties of such materials. We employ an ab initio many-body perturbation theory approach, which explicitly accounts for the excitons and phonons in the heterostructure. Our large-scale first-principles calculations directly probe the role of exciton-phonon coupling in the charge dynamics of the WS2/MoS2 heterobilayer. We find that the exciton-phonon interaction induced relaxation time of photoexcited excitons at the K valley of MoS2 and WS2 is 67 and 15 fs at 300 K, respectively, which sets a lower bound to the intralayer-to-interlayer exciton transfer time and is consistent with experiment reports. We further show that electron-hole correlations facilitate novel transfer pathways that are otherwise inaccessible to noninteracting electrons and holes.

Theory of acoustic-phonon involved exciton spin flip in perovskite semiconductors

We present a theory of the acoustic phonon assisted spin-flip Raman scattering (SFRS), or resonant photoluminescence with the spin flip of a photoexcited exciton localized in a bulk cubic-phase perovskite semiconductor. We consider the spin-flip transitions between the ground-state exciton spin sublevels in external magnetic field B and discuss the variation of their probability rate and polarization selection rules with the increase of B. The transitions are treated as two-quantum processes with the virtual to and fro transfer of the electron in the electron-hole pair between the bottom and first excited conduction bands. The transfer occurs due to both the electron-hole exchange interaction and the electron-phonon interaction. The theoretical results allow one to distinguish the phonon assisted Raman scattering from (a) the resonant Raman scattering with the combined spin flip of the localized resident electron and hole and (b) the biexciton-mediated SFRS analyzed previously.

Giant self-driven exciton-Floquet signatures in time-resolved photoemission spectroscopy of MoS2 from time-dependent GW approach

Time-resolved, angle-resolved photoemission spectroscopy (TR-ARPES) is a one-particle spectroscopic technique that can probe excitons (two-particle excitations) in momentum space. We present an ab initio, time-domain GW approach to TR-ARPES and apply it to monolayer MoS2. We show that photoexcited excitons may be measured and quantified as satellite bands and lead to the renormalization of the quasiparticle bands. These features are explained in terms of an exciton-Floquet phenomenon induced by an exciton time-dependent bosonic field, which are orders of magnitude stronger than those of laser field-induced Floquet bands in low-dimensional semiconductors. Our findings imply a way to engineer Floquet matter through the coherent oscillation of excitons and open the new door for mechanisms for band structure engineering.

Rational Design and Construction of a CdS QDs/InVO4 Atomic‐Layer (110)/(110) Facet S‐Scheme Heterojunction for Highly Efficient Photocatalytic Degradation of C2H4

Exploring high efficiency S‐scheme heterojunction photocatalysts with strong redox ability for removing volatile organic compounds from the air is of great interest and importance. However, how to predict and regulate the transport of photogenerated carriers in heterojunctions is a great challenge. Here, density functional theory calculations were first used to successfully predict the formation of a CdS quantum dots/InVO4 atomic‐layer (110)/(110) facet S‐scheme heterojunction. Subsequently, a CdS quantum dots/InVO4 atomic‐layer was synthesized by in‐situ loading of CdS quantum dots with (110) facets onto the (110) facets of InVO4 atomic‐layer. As a result of the deliberately constructed built‐in electric field between the adjoining facets, we obtain a remarkably enhanced photocatalytic degradation rate for ethylene. This rate is 13.8 times that of pure CdS and 13.2 times that of pure InVO4. In‐situ irradiated X‐ray photoelectron spectroscopy, photoluminescence and time‐resolved photoluminescence measurements were carried out. These experiments validate that the built‐in electric field enhanced the dissociation of photoexcited excitons and the separation of free charge carriers, and results in the formation of S‐scheme charge transfer pathways. The reaction mechanism of the photocatalytic C2H4 oxidation is investigated by in‐situ electron paramagnetic resonance. This work provides a mechanistic insight into the construction and optimization of semiconductor heterojunction photocatalysts for application to environmental remediation.

Solution-Processed NiPS3 Thin Films from Liquid Exfoliated Inks with Long-Lived Spin-Entangled Excitons.

Antiferromagnets are promising materials for future opto-spintronic applications since they show spin dynamics in the THz range and no net magnetization. Recently, layered van der Waals (vdW) antiferromagnets have been reported, which combine low-dimensional excitonic properties with complex spin-structure. While various methods for the fabrication of vdW 2D crystals exist, formation of large area and continuous thin films is challenging because of either limited scalability, synthetic complexity, or low opto-spintronic quality of the final material. Here, we fabricate centimeter-scale thin films of the van der Waals 2D antiferromagnetic material NiPS3, which we prepare using a crystal ink made from liquid phase exfoliation (LPE). We perform statistical atomic force microscopy (AFM) and scanning electron microscopy (SEM) to characterize and control the lateral size and number of layers through this ink-based fabrication. Using ultrafast optical spectroscopy at cryogenic temperatures, we resolve the dynamics of photoexcited excitons. We find antiferromagnetic spin arrangement and spin-entangled Zhang-Rice multiplet excitons with lifetimes in the nanosecond range, as well as ultranarrow emission line widths, despite the disordered nature of our films. Thus, our findings demonstrate scalable thin-film fabrication of high-quality NiPS3, which is crucial for translating this 2D antiferromagnetic material into spintronic and nanoscale memory devices and further exploring its complex spin-light coupled states.

Near-Infrared Photoluminescence from Ytterbium- and Erbium-Codoped CsPbCl3 Perovskite Quantum Dots with Negative Thermal Quenching.

Near-infrared (NIR) luminescent phosphors hold promise for a wide range of applications, from bioimaging to light-emitting diodes (LEDs), but are typically confined to wavelengths <1300 nm and manifest substantial thermal quenching pervasive in luminescent materials. Here we observed the thermally enhanced NIR luminescence of Er3+ (1540 nm), a 2.5-fold enhancement with increasing temperature from 298 to 356 K, from Yb3+- and Er3+-codoped CsPbCl3 perovskite quantum dots (PQDs) (photoexcited at ∼365 nm). Mechanistic investigations revealed that thermally enhanced phenomena originated from combined effects of thermally stable cascade energy transfer (from a photoexcited exciton to a pair of Yb3+ and then to surrounding Er3+) and minimized quenching of surface-adsorbed water molecules on the 4I13/2 state of Er3+ induced by the temperature increase. Importantly, these PQDs enable producing phosphor-converted LEDs emitting at 1540 nm with inherited thermally enhanced properties, having implications for a wide range of photonic applications.

Nano-scale photoexcited exciton mapping: Visualizing molecular orbitals via single molecule’s photocurrent

Photoexcited carriers in semiconductors or molecules can be measured in photocurrent devices as optoelectronic. Incorporationg optical devices with light sources into scanning probe microscopy makes it possible to achieve improved resolution of photocurrent imaging beyond typical microscopic measurements with the optical diffraction limit. Recently, Imai-Imada et al. successfully visualized photocurrent channels from the molecular orbitals of a single molecule at atomic resolution with scanning tunneling microscopy coupled with a narrow-line tunable light source.

Plasmon-exciton couplings in the MoS2/AuNP plasmonic hybrid structure

The understanding and engineering of the plasmon-exciton coupling are necessary to control the innovative optoelectronic device platform. In this study, we investigated the intertwined mechanism of each plasmon-exciton couplings in monolayer molybdenum disulfide (MoS2) and plasmonic hybrid structure. The results of absorption, simulation, electrostatics, and emission spectra show that interaction between photoexcited carrier and exciton modes are successfully coupled by energy transfer and exciton recombination processes. Especially, neutral exciton, trion, and biexciton can be selectively enhanced by designing the plasmonic hybrid platform. All of these results imply that there is another degree of freedom to control the individual enhancement of each exciton mode in the development of nano optoelectronic devices.

Spatially Resolved Local Electronic Properties of 2D Lead Halide Perovskite Single Crystals Studied by X‐Ray Photoemission Electron Microscopy

Recently, research on the edge states of 2D lead halide perovskites (LHPs) has been attracting much attention. The lower‐energy edge state (LES) is believed to provide an efficient pathway for the dissociation of photoexcited excitons. However, the mechanism of the LES formation remains controversial, and studies that establish precisely the local electronic properties are lacking. Herein, the first study of spatially resolved electronic structures in 2D LHP single‐crystal flakes by X‐ray photoemission electron microscopy is presented, specifically identifying the contribution from the edge area. The results show that blueshifts occur in the Pb 5d core‐level peaks at the edge area compared to the interior area with much less difference in I 4d core‐level peaks. The shift becomes more pronounced as n varies from 1 to 3 (≈0.2–1.0 eV). This phenomenon is attributed to the surface restructuring of the edge area induced by the release of mechanical strain through lattice expansion. This work provides an important reference on the origin of the LES of 2D LHPs and is beneficial for future optoelectronic device applications.

Investigation of self-trapped excitonic dynamics in hematite nanoforms through non-degenerate pump–probe transmission spectroscopy

Non-degenerate pump–probe transmission spectroscopy is used to examine the ultrafast dynamics of photo-excited carriers in hematite nanoforms at various pump fluences. Using coupled rate equations, the kinetics of self-trapped exciton (STE) formation and its interaction with free excitons resulting in exciton annihilation were studied. It is shown from this model that the majority of the excitons were trapped by polaronic trap states to form self-trapped excitons within ∼3.5 ps. The findings indicate that free excitons and STEs interact non-linearly, similar to trap-assisted bi-molecular Auger recombination to annihilate one another. It is observed that there is substantial dependence of kinetics of STE formation and exciton decay on photo-excited exciton density, and the nature of this dependence indicates the reduced screening of electron–phonon interaction. Using the screening model applied to the rate constants of STE formation and decay, we estimate the saturation exciton density to be ∼3.3 × 1017 cm−3 and the average STE density to be ∼3.8 × 1018 cm−3 in the hematite nanoforms. We also noticed that doping K and Ni to hematite nanoforms up to 5% did not remarkably change the nature of the exciton dynamics.

Excimer Formation in the Non-Van-Der-Waals 2D Semiconductor Bi2 O2 Se.

The layered semiconductor Bi2 O2 Se is a promising new-type 2D material that holds layered structure via electrostatic forces instead of van der Waals (vdW) attractions. Aside from the huge success in device performance, the non-vdW nature in Bi2 O2 Se with a built-in interlayer electric field has also provided an appealing platform for investigating unique photoexcited carrier dynamics. Here, experimental evidence for the observation of excimers in multilayer Bi2 O2 Se nanosheets via transient absorption spectroscopy is presented. It is found that the excimer formation is the primary decay pathway of photoexcited excitons and three-stage excimer dynamics with corresponding time scales are established. Excitation-fluence-dependent excimer dynamics further suggest that the excimer is diffusive and its formation can be simply described as excitons relaxed to an excimer geometry. This work indicates the outstanding promise of unique excitonic processes in Bi2 O2 Se, which may motivate novel device designs.

Light-induced ferromagnetism in moiré superlattices.

Many-body interactions between carriers lie at the heart of correlated physics. The ability to tune such interactions would allow the possibility to access and control complex electronic phase diagrams. Recently, two-dimensional moiré superlattices have emerged as a promising platform for quantum engineering such phenomena1-3. The power of the moiré system lies in the high tunability of its physical parameters by adjusting the layer twist angle1-3, electrical field4-6, moiré carrier filling7-11 and interlayer coupling12. Here we report that optical excitation can highly tune the spin-spin interactions between moiré-trapped carriers, resulting in ferromagnetic order in WS2 /WSe2 moiré superlattices. Near the filling factor of -1/3 (that is, one hole per three moiré unit cells), as the excitation power at the exciton resonance increases, a well-developed hysteresis loop emerges in the reflective magnetic circular dichroism signal as a function of magnetic field, a hallmark of ferromagnetism. The hysteresis loop persists down to charge neutrality, and its shape evolves as the moiré superlattice is gradually filled, indicating changes of magnetic ground state properties. The observed phenomenon points to a mechanism in which itinerant photoexcited excitons mediate exchange coupling between moiré-trapped holes. This exciton-mediated interaction can be of longer range than direct coupling between moiré-trapped holes9, and thus magnetic order arises even in the dilute hole regime. This discovery adds a dynamic tuning knob to the rich many-body Hamiltonian of moiré quantum matter13-19.

Imaging the effect of high photoexcited densities on valley polarization and coherence in MoS2 monolayers

We have investigated the laser-induced valley polarization and coherence of encapsulated MoS2 monolayer as a function of temperature, power density, and spatial position. Besides a non-monotonic dependence on temperature, recently attributed to a dependence of the valley relaxation time on the momentum scattering rate, we observe a two-fold increase of the valley polarization when increasing the laser excitation power. We attribute this effect to a local heating induced by the energy relaxation of photoexcited excitons and to an increase of the exciton-exciton scattering rate. In contrast, only a moderate enhancement of valley coherence is observed, which exhibits a dramatic drop after further increasing the excitation power. We attribute this behaviour to the detrimental role of exciton-exciton interactions on the pure dephasing rate responsible for the loss of coherence between the valleys. This manifests itself by a strong dip in the spatial profile of the valley coherence at high photoexcited densities.

Dissecting Interlayer Hole and Electron Transfer in Transition Metal Dichalcogenide Heterostructures via Two-Dimensional Electronic Spectroscopy.

Monolayer transition metal dichalcogenides (ML-TMDs) are two-dimensional semiconductors that stack to form heterostructures (HSs) with tailored electronic and optical properties. TMD/TMD-HSs like WS2/MoS2 have type II band alignment and form long-lived (nanosecond) interlayer excitons following sub-100 fs interlayer charge transfer (ICT) from the photoexcited intralayer exciton. While many studies have demonstrated the ultrafast nature of ICT processes, we still lack a clear physical understanding of ICT due to the trade-off between temporal and frequency resolution in conventional transient absorption spectroscopy. Here, we perform two-dimensional electronic spectroscopy (2DES), a method with both high frequency and temporal resolution, on a large-area WS2/MoS2 HS where we unambiguously time resolve both interlayer hole and electron transfer with 34 ± 14 and 69 ± 9 fs time constants, respectively. We simultaneously resolve additional optoelectronic processes including band gap renormalization and intralayer exciton coupling. This study demonstrates the advantages of 2DES in comprehensively resolving ultrafast processes in TMD-HS, including ICT.

Photoinduced phase transition and associated timescales in the excitonic insulator Ta2NiSe5

We investigate the non-equilibrium electronic structure and characteristic time scales in a candidate excitonic insulator, Ta$_2$NiSe$_5$, using time- and angle-resolved photoemission spectroscopy with a temporal resolution of 50 fs. Following a strong photoexcitation, the band gap closes transiently within 100 fs, i.e., on a time scale faster than the typical lattice vibrational period. Furthermore, we find that the characteristic time associated with the rise of the photoemission intensity above the Fermi energy decreases with increasing excitation strength, while the relaxation time of the electron population towards equilibrium shows an opposite behaviour. We argue that these experimental observations can be consistently explained by an excitonic origin of the band gap in the material. The excitonic picture is supported by microscopic calculations based on the non-equilibrium Green's function formalism for an interacting two-band system. We interpret the speedup of the rise time with fluence in terms of an enhanced scattering probability between photo-excited electrons and excitons, leading to an initially faster decay of the order parameter. We show that the inclusion of electron-phonon coupling at a semi-classical level changes only the quantitative aspects of the proposed dynamics, while the qualitative features remain the same. The experimental observations and microscopic calculations allow us to develop a simple and intuitive phenomenological model that captures the main dynamics after photoexcitation in Ta$_2$NiSe$_5$.

Electron-exciton interactions in the exciton-polaron problem

Recently, it has been demonstrated that the absorption of moderately doped two-dimensional semiconductors can be described in terms of exciton polarons. In this scenario, attractive and repulsive polaron branches are formed due to interactions between a photoexcited exciton and a Fermi sea of excess charge carriers. These interactions have previously been treated in a phenomenological manner. Here, we present a microscopic derivation of the electron-exciton interactions which utilizes a mixture of variational and perturbative approaches. We find that the interactions feature classical charge-dipole behavior in the long-range limit, and that they are only weakly modified for moderate doping. We apply our theory to the absorption properties and show that the dependence on doping is well captured by a model with a phenomenological contact potential.

Competition between triplet pair formation and excimer-like recombination controls singlet fission yield

The ultimate goal for singlet fission is that each photo-excited singlet exciton, S1, will result in two triplet excitons with unity yield. However, the singlet fission is now recognized to be complicated, involving bright/dark excited states of different spin multiplicity. Identifying the role of such states is vital to optimize singlet fission yield but difficult due to their elusive spectral signature. Here, we develop an experimental protocol based on a refined magneto-optical probe to access the fast time evolution of various excited states. In diphenylhexatriene crystal, the S1 is found to undergo two competing processes—to form one of the two dark triplet pair intermediates having different exchange energies or to form a bright state, Sx, exhibiting excimer-like delayed photoluminescence. Our result provides a clear picture of a competition event in singlet fission, which is beneficial for the development and tailoring of singlet fission materials with high yield.

Luminescence Behavior and Acceptor Effects of Ambipolar Polymeric Electret on Photorecoverable Organic Field‐Effect Transistor Memory

AbstractPhotorecovery systems are considered to be a potential technology in photosensor, green energy‐saving, and high‐speed communication applications (light‐fidelity). However, the role of photoactive‐electret and semiconductor in the photorecovery system is still unintelligible. Herein, triphenylamine (TPA)‐based donor–acceptor polymers are designed as electrets with more effective excitons dissociation for organic field‐effect transistor memory equipped with photosensitive and photorecoverable response. By modifying TPA‐derived conjugated polymers with various electron‐withdrawing groups (PTPA‐CN, PTPA‐CNBr, and PTPA‐3CN), the obtained PTPAs induce disparate luminescent behaviors in the aggregated state. PTPA‐CN and PTPA‐CNBr exhibit aggregation‐induced emission (AIE) featuring the energy dissipation of partial photoexcited excitons through radiation, while PTPA‐3CN turns to aggregation‐caused quenching (ACQ) behavior leading considerable number of nonemissive excitons which can directly recombine with charged medium, an electret containing trapped charges. Pentacene‐based transistor devices incorporated with studied photoactive electrets are constructed for mechanism investigation. The results demonstrate that photorecovery response ability of ACQ‐polymer displays much faster than that of AIE‐polymers, PTPA‐CN, and PTPA‐CNBr, upon UV light irradiation, attributing to the intensely electron‐withdrawing ability of acceptor attached on the conjugated skeleton. The ACQ‐electret device behaves superior memory switching performance with reliable endurance characteristics under the cycling stress of electrical‐programming and optical‐erasing operations, demonstrating the feasibility for organic optoelectronic applications.

Probing Excitons in Ultrathin PbS Nanoplatelets with Enhanced Near-Infrared Emission.

Colloidal PbS nanoplatelets (NPLs) are highly interesting materials for near-infrared optoelectronic applications. We use ultrafast transient optical absorption spectroscopy to study the characteristics and dynamics of photoexcited excitons in ultrathin PbS NPLs with a cubic crystal structure. NPLs are synthesized at near room temperature from lead oleate and thiourea precursors; they show an optical absorption onset at 680 nm (1.8 eV) and photoluminescence at 720 nm (1.7 eV). By postsynthetically treating PbS NPLs with CdCl2, their photoluminescence quantum yield is strongly enhanced from 1.4% to 19.4%. The surface treatment leads to an increased lead to sulfur ratio in the structures and associated reduced nonradiative recombination. Additionally, exciton-phonon interactions in pristine and CdCl2 treated NPLs at frequencies of 1.96 and 2.04 THz are apparent from coherent oscillations in the transient absorption spectra. This study is an important step forward in unraveling and controlling the optical properties of IV-VI semiconductor NPLs.

Direct formation of interlayer exciton in two-dimensional van der Waals heterostructures.

In atomically thin two-dimensional van der Waals (2D vdW) heterostructures, spatially separated interlayer excitons play an important role in the optoelectronic performance and show great potential for the exploration of many-body quantum phenomena. A commonly accepted formation mode for interlayer excitons is via a two-step intralayer exciton transfer mechanism, namely, photo-excited intralayer excitons are initially generated in individual sublayers, and photogenerated electrons and holes are then separated into opposite sublayers based on the type-II band alignment. Herein, we expand the concept of interlayer exciton formation and reveal that bright interlayer excitons can be generated in one step by direct interlayer photoexcitation in 2D vdW heterostructures that have strong interlayer coupling and a short photoexcitation channel. First-principles and many-body perturbation theory calculations demonstrate that indium selenide/antimonene and indium selenide/black phosphorus heterostructures are two promising systems that show an exceptionally large interlayer transition probability (>500 Debye2). This study enriches the understanding of interlayer exciton formation and provides a new avenue to acquiring strong interlayer excitons in artificial 2D vdW heterostructures.