Exciton Lifetime and Optical Line Width Profile via Exciton-Phonon Interactions: Theory and First-Principles Calculations for Monolayer MoS2.

Exciton dynamics dictates the evolution of photoexcited carriers in photovoltaic and optoelectronic devices. However, interpreting their experimental signatures is a challenging theoretical problem due to the presence of both electron-phonon and many-electron interactions. We develop and apply here a first-principles approach to exciton dynamics resulting from exciton-phonon coupling in monolayer MoS2 and reveal the highly selective nature of exciton-phonon coupling due to the internal spin structure of excitons, which leads to a surprisingly long lifetime of the lowest-energy bright A exciton. Moreover, we show that optical absorption processes rigorously require a second-order perturbation theory approach, with photon and phonon treated on an equal footing, as proposed by Toyozawa and Hopfield. Such a treatment, thus far neglected in first-principles studies, gives rise to off-diagonal exciton-phonon self-energy, which is critical for the description of dephasing mechanisms and yields exciton line widths in excellent agreement with experiment.

Suppressing Exciton-Vibration Coupling to Prolong Exciton Lifetime of Nonfullerene Acceptors Enables High-Efficiency Organic Solar Cells.

The limited exciton lifetime (τ, generally <1 ns) leads to short exciton diffusion length (LD ) of organic semiconductors, which is the bottleneck issue impeding the further improvement of power conversion efficiencies (PCEs) for organic solar cells (OSCs). However, efficient strategies to prolong intrinsic τ are rare and vague. Herein, we propose a facile method to efficiently reduce vibrational frequency of molecular skeleton and suppress exciton-vibration coupling to decrease non-radiative decay rate and thus prolong τ via deuterating nonfullerene acceptors. The τ remarkably increases from 0.90 ns (non-deuterated L8-BO) to 1.35 ns (deuterated L8-BO-D), which is the record for organic photovoltaic materials. Besides, the inhibited molecular vibration improves molecular planarity of L8-BO-D for enhanced exciton diffusion coefficient. Consequently, the LD increases from 7.9 nm (L8-BO) to 10.7 nm (L8-BO-D). The prolonged LD of L8-BO-D enables PM6 : L8-BO-D-based bulk heterojunction OSCs to acquire higher PCEs of 18.5 % with more efficient exciton dissociation and weaker charge carrier recombination than PM6 : L8-BO-based counterparts. Moreover, benefiting from the prolonged LD , D18/L8-BO-D-based pseudo-planar heterojunction OSCs achieve an impressive PCE of 19.3 %, which is among the highest values. This work provides an efficient strategy to increase the τ and thus LD of organic semiconductors, boosting PCEs of OSCs.

Nanocavity Clock Spectroscopy: Resolving Competing Exciton Dynamics in WSe2/MoSe2 Heterobilayers.

Transition-metal dichalcogenide heterostructures are an emergent platform for novel many-body states from exciton condensates to nanolasers. However, their exciton dynamics are difficult to disentangle due to multiple competing processes with time scales varying over many orders of magnitude. Using a configurable nano-optical cavity based on a plasmonic scanning probe tip, the radiative (rad) and nonradiative (nrad) relaxation of intra- and interlayer excitons is controlled. Tuning their relative rates in a WSe2/MoSe2 heterobilayer over 6 orders of magnitude in tip-enhanced photoluminescence spectroscopy reveals a cavity-induced crossover from nonradiative quenching to Purcell-enhanced radiation. Rate equation modeling with the interlayer charge transfer time as a reference clock allows for a comprehensive determination from the long interlayer exciton (IX) radiative lifetime τIXrad = (94 ± 27) ns to the 5 orders of magnitude faster competing nonradiative lifetime τIXnrad = (0.6 ± 0.2) ps. This approach of nanocavity clock spectroscopy is generally applicable to a wide range of excitonic systems with competing decay pathways.

Long-Lived Direct and Indirect Interlayer Excitons in van der Waals Heterostructures.

We report the observation of a doublet structure in the low-temperature photoluminescence of interlayer excitons in heterostructures consisting of monolayer MoSe2 and WSe2. Both peaks exhibit long photoluminescence lifetimes of several tens of nanoseconds up to 100 ns verifying the interlayer nature of the excitons. The energy and line width of both peaks show unusual temperature and power dependences. While the low-energy peak dominates the spectra at low power and low temperatures, the high-energy peak dominates for high power and temperature. We explain the findings by two kinds of interlayer excitons being either indirect or quasi-direct in reciprocal space. Our results provide fundamental insights into long-lived interlayer states in van der Waals heterostructures with possible bosonic many-body interactions.

Localized Gradual Photomediated Brightness and Lifetime Increase of Superacid-Treated Monolayer MoS2.

Monolayer semiconducting transition-metal dichalcogenides (S-TMDs) have been extensively studied as materials for next-generation optoelectronic devices due to their direct band gap and high exciton binding energy at room temperature. Under a superacid treatment of bis(trifluoromethane)sulfonimide (TFSI), sulfur-based TMDs such as MoS2 can emit strong photoluminescence (PL) with a photoluminescence quantum yield (PLQY) approaching unity. However, the magnitude of PL enhancement varies by more than 2 orders of magnitude in published reports. A major culprit behind the discrepancy is sulfur-based TMD's sensitivity to above-bandgap photostimulation. Here, we present a detailed study of how TFSI-treated MoS2 reacts to photostimulation with increasing PL occurring hours after continuous or pulsed laser exposure. The PL of TFSI-treated MoS2 is enhanced up to 74 times its initial intensity after 5 h of continuous exposure to 532 nm laser light. Photostimulation also enhances the PL of untreated MoS2 but with a much smaller enhancement. Caution should be taken when probing MoS2 PL spectra, as above-bandgap light can alter the resulting intensity and peak wavelength of the emission over time. The presence of air is verified to play a key role in the photostimulated enhancement effect. Additionally, the rise of PL intensity is mirrored by an increase in measured carrier lifetime of up to ∼400 ps, consistent with the suppression of nonradiative pathways. This work demonstrates why variations in PL intensity are observed across samples and provides an understanding of the changes in carrier lifetimes to better engineer next-generation optoelectronic devices.

GaAs Cone-Shell Quantum Dots in a Lateral Electric Field: Exciton Stark-Shift, Lifetime, and Fine-Structure Splitting.

Strain-free GaAs cone-shell quantum dots have a unique shape, which allows a wide tunability of the charge-carrier probability densities by external electric and magnetic fields. Here, the influence of a lateral electric field on the optical emission is studied experimentally using simulations. The simulations predict that the electron and hole form a lateral dipole when subjected to a lateral electric field. To evaluate this prediction experimentally, we integrate the dots in a lateral gate geometry and measure the Stark-shift of the exciton energy, the exciton intensity, the radiative lifetime, and the fine-structure splitting (FSS) using single-dot photoluminescence spectroscopy. The respective gate voltage dependencies show nontrivial trends with three pronounced regimes. We assume that the respective dominant processes are charge-carrier deformation at a low gate voltage U, a vertical charge-carrier shift at medium U, and a lateral charge-carrier polarization at high U. The lateral polarization forms a dipole, which can either enhance or compensate the intrinsic FSS induced by the QD shape anisotropy, dependent on the in-plane orientation of the electric field. Furthermore, the data show that the biexciton peak can be suppressed by a lateral gate voltage, and we assume the presence of an additional vertical electric field induced by surface charges.

Synergetic Enhancement of Quantum Yield and Exciton Lifetime of Monolayer WS2 by Proximal Metal Plate and Negative Electric Bias.

The efficiency of light emission is a critical performance factor for monolayer transition metal dichalcogenides (1L-TMDs) for photonic applications. While various methods have been studied to compensate for lattice defects to improve the quantum yield (QY) of 1L-TMDs, exciton-exciton annihilation (EEA) is still a major nonradiative decay channel for excitons at high exciton densities. Here, we demonstrate that the combined use of a proximal Au plate and a negative electric gate bias (NEGB) for 1L-WS2 provides a dramatic enhancement of the exciton lifetime at high exciton densities with the corresponding QY enhanced by 30 times and the EEA rate constant decreased by 80 times. The suppression of EEA by NEGB is attributed to the reduction of the defect-assisted EEA process, which we also explain with our theoretical model. Our results provide a synergetic solution to cope with EEA to realize high-intensity 2D light emitters using TMDs.

Role of Exciton Lifetime, Energetic Offsets, and Disorder in Voltage Loss of Bulk Heterojunction Organic Solar Cells.

Recently, the power conversion efficiency (PCE) of organic solar cells (OSCs) has significantly progressed with a rapid increase from 10 to 19% due to state-of-the-art research on nonfullerene acceptor molecules and various device processing strategies. However, OSCs still exhibit significant open circuit voltage loss (ΔVOC ∼ 0.6 V) due to high energetic offsets and molecular disorder. In this work, we present a systematic investigation to determine the effects of energetic offset and disorder on different recombination losses in open circuit voltage (VOC) using 13 different photoactive layers, wherein the PCE and ΔVOC vary in the ranges of 2.21-14.74% and 0.561-1.443 V, respectively. The detailed voltage loss analysis of all these devices was carried out, and voltage losses were correlated with energetic offset and disorder. This has enabled us to identify the key features for minimizing the voltage loss like: (1) a low energy offset between the donor and acceptor molecular states is essential to attain a nonradiative voltage loss (ΔVOC, nrad) as low as ∼200 meV and (2) Urbach energy, which is a measure of the materials' disorder and packing, should be low for the minimization of the radiative voltage loss (ΔVOC, rad). In addition, time-resolved photoluminescence spectroscopy was employed to further understand the exciton dynamics of pristine materials and donor-acceptor blends. It was observed that the absorbers with ultralong exciton lifetime (∼1000 ps) produce higher efficiencies. The current study emphasizes the importance of simultaneously testing photovoltaic performance and active layer exciton dynamics for rational device optimization and opens new prospects for designing novel molecules with fine-tuning of energetic offset and disorder with longer exciton lifetime which is the effective strategy to boost the efficiency of OSCs to their modified Shockley-Queisser (SQ) limit by minimizing radiative and nonradiative voltage losses.

Strong Electric Polarizability of Cone-Shell Quantum Structures for a Large Stark Shift, Tunable Long Exciton Lifetimes, and a Dot-to-Ring Transformation.

Strain-free GaAs cone-shell quantum structures (CSQS) with widely tunable wave functions (WF) are fabricated using local droplet etching (LDE) during molecular beam epitaxy (MBE). During MBE, Al droplets are deposited on an AlGaAs surface, which then drill low-density (about 1 × 107 cm-2) nanoholes with adjustable shape and size. Subsequently, the holes are filled with GaAs to form CSQS, where the size can be adjusted by the amount of GaAs deposited for hole filling. An electric field is applied in growth direction to tune the WF in a CSQS. The resulting highly asymmetric exciton Stark shift is measured using micro-photoluminescence. Here, the unique shape of the CSQS allows a large charge-carrier separation and, thus, a strong Stark shift of up to more than 16 meV at a moderate field of 65 kV/cm. This corresponds to a very large polarizability of 8.6 × 10-6 eVkV -2 cm2. In combination with simulations of the exciton energy, the Stark shift data allow the determination of the CSQS size and shape. Simulations of the exciton-recombination lifetime predict an elongation up to factor of 69 for the present CSQSs, tunable by the electric field. In addition, the simulations indicate the field-induced transformation of the hole WF from a disk into a quantum ring with a tunable radius from about 10 nm up to 22.5 nm.

Engineering the Dynamics and Transport of Excitons, Trions, and Biexcitons in Monolayer WS2.

The study of transport and diffusion dynamics of quasi-particles such as excitons, trions, and biexcitons in two-dimensional (2D) semiconductors has opened avenues for their application in high-speed excitonic and optoelectronic devices. However, long-range transport and fast diffusion of these quasi-particles have not been reported for 2D systems such as transition metal dichalcogenides (TMDCs). The reported diffusion coefficients from TMDCs are low, limiting their use in high-speed excitonic devices and other optoelectronic applications. Here, we report the highest exciton diffusion coefficient value in monolayer WS2 achieved via engineering the radiative lifetime and diffusion lengths using static back-gate voltage and substrate engineering. Electrostatic doping is observed to modulate the radiative lifetime and in turn the diffusion coefficient of excitons by ∼three times at room temperature. By combining electrostatic doping and substrate engineering, we push the diffusion coefficient to an extremely high value of 86.5 cm2/s, which has not been reported before in TMDCs and is even higher than the values in some 1D systems. At low temperatures, we further report the control of dynamic and spatial diffusion of excitons, trions, and biexcitons from WS2. The electrostatic control of dynamics and transport of these quasi-particles in monolayers establishes monolayer TMDCs as ideal candidates for high-speed excitonic circuits, optoelectronic, and photonic device applications.

Interlayer Exciton Transport in MoSe2/WSe2 Heterostructures.

A moiré superlattice formed by stacking two lattice mismatched transition metal dichalcogenide monolayers, functions as a diffusion barrier that affects the energy transport and dynamics of interlayer excitons (electron and hole spatially concentrated in different monolayers). In this work, we experimentally quantify the diffusion barrier experienced by interlayer excitons in hexagonal boron nitride-encapsulated molybdenum diselenide/tungsten diselenide (MoSe2/WSe2) heterostructures with different twist angles. We observe the localization of interlayer excitons at low temperature and the temperature-activated diffusivity as a function of twist angle and hence attribute it to the deep periodic potentials arising from the moiré superlattice. We further support the observations with theoretical calculations, Monte Carlo simulations, and a three-level model that represents the exciton dynamics at various temperatures.

Enhanced Room-Temperature Photoluminescence Quantum Yield in Morphology Controlled J-Aggregates.

Supramolecular assemblies from organic dyes forming J-aggregates are known to exhibit narrowband photoluminescence with full-width at half maximum of ≈9 nm (260 cm-1). Applications of these high color purity emitters, however, are hampered by the rather low photoluminescence quantum yields reported for cyanine J-aggregates, even when formed in solution. Here, it is demonstrated that cyanine J-aggregates can reach an order of magnitude higher photoluminescence quantum yield (increase from 5% to 60%) in blend solutions of water and alkylamines at room temperature. By means of time-resolved photoluminescence studies, an increase in the exciton lifetime as a result of the suppression of non-radiative processes is shown. Small-angle neutron scattering studies suggest a necessary condition for the formation of such highly emissive J-aggregates: the presence of a sharp water/amine interface for J-aggregate assembly and the coexistence of nanoscale-sized water and amine domains to restrict the J-aggregate size and solubilize monomers, respectively.

Inorganic Ruddlesden-Popper Faults in Cesium Lead Bromide Perovskite Nanocrystals for Enhanced Optoelectronic Performance.

While the layered hybrid Ruddlesden-Popper (RP) halide perovskites have already established themselves as the frontrunners among the candidates in optoelectronics, their all-inorganic counterparts remain least explored in the RP-type perovskite family. Herein, we study and compare the optoelectronic properties of all-inorganic CsPbBr3 perovskite nanocrystals (PNCs) with and without RP planar faults. We find that the RP-CsPbBr3 PNCs possess both higher exciton binding energy and longer exciton lifetimes. The former is ascribed to a quantum confinement effect in the PNCs induced by the RP faults. The latter is attributed to a spatial electron-hole separation across the RP faults. A striking difference is found in the up-conversion photoluminescence response in the two types of CsPbBr3 PNCs. For the first time, all-inorganic RP-CsPbBr3 PNCs are tested in light-emitting devices and shown to significantly outperform the non-RP CsPbBr3 PNCs.

Substrate effect on excitonic shift and radiative lifetime of two-dimensional materials.

Substrates have strong effects on optoelectronic properties of two-dimensional (2D) materials, which have emerged as promising platforms for exotic physical phenomena and outstanding applications. To reliably interpret experimental results and predict such effects at 2D interfaces, theoretical methods accurately describing electron correlation and electron-hole interaction such as first-principles many-body perturbation theory are necessary. In our previous work (2020Phys. Rev. B102205113), we developed the reciprocal-space linear interpolation method that can take into account the effects of substrate screening for arbitrarily lattice-mismatched interfaces at the GW level of approximation. In this work, we apply this method to examine the substrate effect on excitonic excitation and recombination of 2D materials by solving the Bethe-Salpeter equation. We predict the nonrigid shift of 1s and 2s excitonic peaks due to substrate screening, in excellent agreements with experiments. We then reveal its underlying physical mechanism through 2D hydrogen model and the linear relation between quasiparticle gaps and exciton binding energies when varying the substrate screening. At the end, we calculate the exciton radiative lifetime of monolayer hexagonal boron nitride with various substrates at zero and room temperature, as well as the one of WS2where we obtain good agreement with experimental lifetime. Our work answers important questions of substrate effects on excitonic properties of 2D interfaces.

Efficient Exciton Diffusion in Micrometer-Sized Domains of Nanographene-Based Nonfullerene Acceptors with Long Exciton Lifetimes in Blend Films with Conjugated Polymer.

Phase-separated structures in photoactive layers composed of electron donors and acceptors in organic photovoltaics (OPVs) generally exert a profound impact on the device performance. In this study, nonfullerene acceptors (NFAs) where a heteronanographene central core was furnished with branched alkoxy chains of different lengths, TACIC-EH, TACIC-BO, and TACIC-HD, were prepared to adjust the aggregation tendency and systematically probe the relationships of film structures with photophysical and photovoltaic properties. The side-chain length showed negligible effects on the absorption properties and energy levels of TACICs. In addition, regardless of the chain length, all TACIC films exhibited characteristically long singlet exciton lifetimes (1330-2330 ps) compared to those in solution (≤220 ps). Using a conjugated polymer donor, PBDB-T, the best OPV performance was achieved with TACIC-BO that contained medium-length chains, exhibiting a power conversion efficiency (PCE) of 9.92%. TACIC-HD with the longest chains showed deteriorated electron mobility due to the long insulating alkoxy groups. Therefore, the PBDB-T:TACIC-HD-based device revealed a low charge collection efficiency and PCE (8.21%) relative to the PBDB-T:TACIC-BO-based device, but their film morphologies were analogous. Meanwhile, TACIC-EH with the shortest chains showed low solubility and formed micrometer-sized large aggregates in the blend film with PBDB-T. Although the charge collection efficiency of PBDB-T:TACIC-EH was lower than that of PBDB-T:TACIC-BO, the efficiencies of exciton diffusion to the donor-acceptor interface were sufficiently high (>98%) owing to the elongated singlet exciton lifetime of TACIC-EH. The PCE of the PBDB-T:TACIC-EH-based device remained moderate (7.10%). Therefore, TACICs with the long singlet exciton lifetimes in the films provide a clear guideline for NFAs with low sensitivity of OPV device performance to the blend film structures, which is advantageous for large-scale OPV production with high reproducibility.

Limitations and Perspectives on Triplet-Material-Based Organic Photovoltaic Devices.

Organic photovoltaic cells (OPVs) have attracted broad attention and become a very energetic field after the emergence of nonfullerene acceptors. Long-lifetime triplet excitons are expected to be good candidates for efficiently harvesting a photocurrent. Parallel with the development of OPVs based on singlet materials (S-OPVs), the potential of triplet materials as photoactive layers has been explored. However, so far, OPVs employing triplet materials in a bulk heterojunction have not exhibited better performance than S-OPVs. Here, the recent progress of representative OPVs based on triplet materials (T-OPVs) is briefly summarized. Based on that, the performance limitations of T-OPVs are analyzed. The shortage of desired triplet materials with favorable optoelectronic properties for OPVs, the tradeoff between long lifetime and high binding energy of triplet excitons, as well as the low charge mobility in most triplet materials are crucial issues restraining the efficiencies of T-OPVs. To overcome these limitations, first, novel materials with desired optoelectronic properties are urgently demanded; second, systematic investigation on the contribution and dynamics of triplet excitons in T-OPVs is necessary; third, close multidisciplinary collaboration is required, as proved by the development of S-OPVs.

Achieving Enhanced Thermally Activated Delayed Fluorescence Rates and Shortened Exciton Lifetimes by Constructing Intramolecular Hydrogen Bonding Channels.

A fast radiative rate, highly suppressed nonradiation, and a short exciton lifetime are key elements for achieving efficient thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) with reduced efficiency roll-off at a high current density. Herein, four representative TADF emitters are designed and synthesized based on the combination of benzophenone (BP) or 3-benzoylpyridine (BPy3) acceptors, with dendritic 3,3″,6,6″-tetra-tert-butyl-9'H-9,3':6',9″-tercarbazole (CDTC) or 10H-spiro(acridine-9,9'-thioxanthene) (TXDMAc) donors, respectively. Density functional theory simulation and X-ray diffraction analysis validated the formation of CH···N intramolecular hydrogen bonds regarding the BPy3-CDTC and BPy3-TXDMAc compounds. Notably, the construction of intramolecular hydrogen bonding within TADF emitters significantly enhances the intramolecular charge transfer (ICT) strength while reducing the donor-acceptor (D-A) dihedral angle, resulting in accelerated radiative and suppressed nonradiative processes. With short TADF exciton lifetimes (τTADF) and high photoluminescence quantum yields (ϕPL), OLEDs employing BPy3-CDTC and BPy3-TXDMAc dopants realized maximum external quantum efficiencies (EQEs) up to 18.9 and 25.6%, respectively. Moreover, the nondoped device based on BPy3-TXDMAc exhibited a maximum EQE of 18.7%, accompanied by an extremely small efficiency loss of only 4.1% at the luminance of 1000 cd m-2. In particular, the operational lifetime of the sky-blue BPy3-CDTC-based device was greatly extended by 10 times in contrast to the BP-CDTC-based counterpart, verifying the idea that the in-built intramolecular hydrogen bonding strategy was promising for the realization of efficient and stable TADF-OLEDs.

Efficient Generation of Long-Lived Triplet Excitons in 2D Hybrid Perovskite.

Triplet excitons form in quasi-2D hybrid inorganic-organic perovskites and diffuse over 100 nm before radiating with >11% photoluminescence quantum efficiency (PLQE) at low temperatures.