Tunable Valley Pseudospin and Electron-Phonon Coupling in WSe2/1T-VSe2 Heterostructures.

Heterostructure engineering provides versatile platforms for exploring exotic physics and enhancing the device performance through interface coupling. Despite the rich array of physical phenomena presented by heterostructures composed of semiconductor and metal van der Waals materials, significant gaps remain in understanding their optical, thermal, and electronic properties. Here, we demonstrate that the valley pseudospin and electron-phonon coupling in monolayer WSe2 are significantly influenced by interface coupling with 1T-VSe2. The heterointerface alters the relaxation process of valley excitons, leading to a transition in magnetic-field-dependent valley polarization from a linear to a "V" shape. Furthermore, we uncover that enhanced electron-phonon coupling exacerbates variations in exciton and valley exciton behavior with temperature, involving higher phonon energies and a shift from acoustic to optical phonons. These findings highlight a promising pathway to manipulate valley excitons and investigate electron-phonon coupling through van der Waals interface interactions.

6-Methoxy-2-Naphthoate as a Standard Chromophore for Chiroptical Studies by Fluorescence-Detected Exciton-Coupled Circular Dichroism.

This study investigated the applicability of fluorescent chromophores for exciton-coupled circular dichroism (ECCD) exploiting fluorescence-detected circular dichroism (FDCD). FDCD had been previously reported useful in allowing the sensitive detection of ECCD in favorable conditions. However, fluorescence detection may prevent applications of the combined method especially when solutions are polarized in emission. Even without polarization of emission, FDCD deviates from circular dichroism (CD) in some cases when the fluorophore of interest interacts with nonfluorescent chromophore. Herein, it was confirmed that employing 6-methoxy-2-naphthoate always yielded interpretable exciton-coupled FDCD spectra even when coupling with nonfluorescent p-substituted benzoates. The 6-methoxy-2-naphthoate chromophore (6-MN) is prescribed in special cases when only a small amount of sample is available for determining the absolute stereochemistry by the CD exciton chirality method observed by FDCD.

Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2.

2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long-lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long-range opto-electronic behavior in van der Waals materials through molecular synthetic chemistry.

Visualizing Triplet Energy Transfer in Organic Near-Infrared Phosphorescent Host-Guest Materials.

Limited by the energy gap law, purely organic materials with efficient near-infrared room temperature phosphorescence are rare and difficult to achieve. Additionally, the exciton transition process among different emitting species in host-guest phosphorescent materials remains elusive, presenting a significant academic challenge. Herein, using a modular nonbonding orbital-π bridge-nonbonding orbital (n-π-n) molecular design strategy, we develop a series of heavy atom-free phosphors. Systematic modification of the π-conjugated cores enables the construction of a library with tunable near-infrared phosphorescence from 655 to 710 nm. These phosphors exhibit excellent performance under ambient conditions when dispersed into a 4-bromobenzophenone host matrix, achieving an extended lifetime of 11.25 ms and a maximum phosphorescence efficiency of 4.2%. Notably, by eliminating the interference from host phosphorescence, the exciton transition process can be visualized in hybrid materials under various excitation conditions. Spectroscopic analysis reveals that the improved phosphorescent performance of the guest originates from the triplet-triplet energy transfer of abundant triplet excitons generated independently by the host, rather than from enhanced intersystem crossing efficiency between the guest singlet state and the host triplet state. The findings provide in-depth insights into constructing novel near-infrared phosphors and exploring emission mechanisms of host-guest materials.

Donor polarization engineering of conjugated microporous polymers to boost exciton dissociation for photocatalytic degradation of tetracycline.

The misuse and inevitable release of antibiotics can cause significant harm to both human health and the environment, and the use of polymeric semiconductors for photodegradation of antibiotics in aqueous environments is one of the most effective strategies to alleviate the current dilemma. Nevertheless, the inherently high exciton binding energy (Eb) and low photogenerated carrier transfer efficiency for most photocatalysts results in unsatisfactory photodegradation performance. Hence, this work proposes a donor polarization strategy to regulate the exciton dissociation of conjugated microporous polymers (CMPs) by minimizing their Eb. Results exhibited that the introduction of the strong donor unit 3,4-ethylenedioxythiophene (EDOT) not only reduces the Eb and effectively promotes exciton dissociation, but also broadens the visible light absorption of CMP. Among them, EdtTz-CMP with the lowest Eb (99 meV) delivered an efficiency of 94.6% in photocatalytic degradation of tetracycline (TC) with in 90 min, significantly higher than those of its analogues. This work provides a viable approach to design CMPs by tuning the intrinsic dipole of the donor for efficient environmental purification.

Interlayer Exciton-Phonon Coupling in MoSe2/WSe2 Heterostructures.

Transition metal dichalcogenide heterostructures have garnered strong interest for their robust excitonic properties, mixed light-matter states such as exciton-polaritons, and tailored properties, vital for advanced device engineering. Two-dimensional heterostructures inherit their physics from monolayers with the addition of interlayer processes that have been particularly emphasized for their electronic and optical properties. Here, we demonstrate the interlayer coupling of the MoSe2 phonons to WSe2 excitons in a WSe2/MoSe2 heterostructure using resonant Raman scattering. The WSe2 monolayer induces an interlayer resonance in the Raman cross-section of the MoSe2 A1g phonons. Frozen-phonon calculations within density functional theory reveal a strong deformation-potential coupling between the A1g MoSe2 phonon and the electronic states of the close-by WSe2 layer approaching 20% of the intralayer coupling to the MoSe2 electrons. Understanding the vibrational properties of van der Waals heterostructures requires going beyond the sum of their constituents and considering cross-material coupling.

Long-Range Ballistic Propagation of 80% Excitonic Fraction Polaritons in a Perovskite Metasurface at Room Temperature.

Exciton-polaritons, hybrid light-matter excitations arising from the strong coupling between excitons in semiconductors and photons in photonic nanostructures, are crucial for exploring the physics of quantum fluids of light and developing all-optical devices. Achieving room temperature propagation of polaritons with a large excitonic fraction is challenging but vital, e.g., for nonlinear light transport. We report on room temperature propagation of exciton-polaritons in a metasurface made from a subwavelength lattice of perovskite pillars. The large Rabi splitting, much greater than the optical phonon energy, decouples the lower polariton band from the phonon bath of the perovskite. These cooled polaritons, in combination with the high group velocity achieved through the metasurface design, enable long-range propagation, exceeding hundreds of micrometers even with an 80% excitonic component. Furthermore, the design of the metasurface introduces an original mechanism for unidirectional propagation through polarization control, suggesting a new avenue for the development of advanced polaritonic devices.

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.

Quantum control of polariton emission in a microcavity-quantum well system under magnetic field.

In this work, a quantum dissipative model is employed to investigate the influence of a perpendicular magnetic field on the photoluminescence (PL) spectrum of a quantum well embedded within a microcavity. This model incorporates both the exact electron-hole interaction within the semiconductor and the light-matter coupling between the fundamental photonic mode and the fermionic particles. The loss and pumping mechanisms are described using the quantum master equation, and the PL spectrum is determined via the quantum regression theorem. Our findings demonstrate that the magnetic field acts as a control mechanism in the polariton emission energy, the emission linewidth and the intensity distribution along the emission line. Finally, it is observed that the magnetic field can redistribute the density matrix occupations leading to modifications in the average number of polaritons in the system.

An RNA aptamer photoelectrochemical biosensor based on the exciton energy transfer constructed for theophylline detection.

A novel photoelectrochemical (PEC) biosensor was developed incorporating a specifically designed RNA aptamer for the detection of theophylline (TP). This involved utilizing two nucleotide base aptamers with tailored sequences designed to target TP. The 3' end of a single-stranded RNA sequence (5'-GGAUACCA-(CH2)6-SH-3') and the 5' end of a complementary stranded RNA sequence (5'-HS-(CH2)6-CCUUGGAAGCC-3') were linked to gold nanoparticles (AuNPs) and CdS quantum dots (QDs), respectively. These two single-stranded RNAs (ssRNA) formed a double-stranded RNA (dsRNA) capable of recognizing TP. This major structural change altered the spacing between QDs and NPs, which signaled the presence and concentration of TP. TP was photoelectrochemical catalytic oxidation by the hole of CdS QDs under illumination, then anode photocurrent was generated. Due to the increase in surface impedance and the effect of exciton energy transfer (EET) between QDs and AuNPs, the photocurrent would undergo varying degrees of change. TP was detected by changes in photocurrent. PEC detection of TP was achieved in the range of 0.1 µM-200 µM. The detection limit was 0.033 µM. The method exhibited commendable reproducibility and remarkable selectivity. The biosensor was used to measure TP content in tea, beverages and blood samples, resulting in satisfactory recovery rates.

Controllable Multi-exciton Zero-dimensional Antimony-based Metal Halides for White-light Emission and ß-ray Detection.

Self-trapped exciton (STE) emission, typified by antimony (Sb), with broadband characteristics, represents the next generation of materials for solid-state lighting and radiation detection. However, little is known about the multiexciton behavior of the Sb emission center. Here, we proposed a general approach for designing antimony-centered multi-exciton emitting materials through self-assembly. Benefitting from controllable multiexciton behavior, dual-band white light emission spanning the entire visible spectrum was achieved. Relying on the reduction of an effective atomic number brought by self-assembly, excellent scintillation response to ß-rays was attained. This study offers unprecedented insight into hybrid single/triple STE emission and unveils new avenues for single-emitter white-light emission, as well as radiographic testing using low-risk ß-rays as sources.

Augmented Extraction Efficiency of a Hot D Exciton in MoS2 via Intervalley Scattering.

Prolonging hot carrier cooling, a crucial factor in optoelectronic applications, including hot carrier photovoltaics, presents a significant challenge. High-energy band-nesting excitons within parallel bands offer a promising and underexplored avenue for addressing this issue. Here, we exploit an exceptional D exciton cooling prolongation of 2 to 3 orders of magnitude compared to sub-picosecond in typical transition metal dichalcogenides (TMDs) owing to the complex Coulomb environment and the sequential and mismatch-valley relaxation. Simultaneously, the intervalley scattering upconversion of band-edge excitons with the slow D exciton formation in the metastable Γ valley/hill also reduces the cooling rate. We successfully extract D and C excitons as hot carriers through integrating with various thicknesses of TiOx, achieving the highest efficiency of 98% and 85% at a Ti thickness of 2 nm. Our findings highlight the potential of band-nesting excitons for extending hot carrier cooling time, paving the way for advancements in hot carrier-based optoelectronic devices.

Polarization-Controlled Exciton-Polaritons in WS2 Strongly Coupled with Low-Symmetry Photonic Crystal Nanostructures.

Atomically thin transition metal dichalcogenides (TMDs) with ambient stable exciton resonances have emerged as an ideal material platform for exciton-polaritons. In particular, the strong coupling between excitons in TMDs and optical resonances in anisotropic photonic nanostructures can form exciton-polaritons with polarization selectivity, which offers a new degree of freedom for the manipulation of the light-matter interaction. In this work, we present the experimental demonstration of polarization-controlled exciton-polaritons in tungsten disulfide (WS2) strongly coupled with polarization singularities in the momentum space of low-symmetry photonic crystal (PhC) nanostructures. The utilization of polarization singularities can not only effectively modulate the polarization states of exciton-polaritons in the momentum space but also facilitate or suppress their far field coupling capabilities by tuning the in-plane momentum. Our results provide new strategies for creating polarization-selective exciton-polaritons.

Rational Molecular Design of Phenanthroimidazole-Based Fluorescent Materials toward High-Efficiency Deep-Blue OLEDs by Molecular Isomer Engineering.

Organic light-emitting diodes (OLEDs) have been extensively investigated in full-color displays and energy-saving lighting owing to their unique advantages. However, deep-blue OLEDs based on nondoped emitting layers with a satisfactory external quantum efficiency (EQE) are still rare for applications. In this work, six hot exciton materials, PPIM-12F, PPIM-22F, PPIM-13F, PPIM-23F, PPIM-1CN, and PPIM-2CN, are designed and synthesized via an isomer engineering design strategy and their photophysical properties and OLED performance are systematically investigated. These emitters all possess wide band gaps (3.53-3.69 eV), hybrid local and charge transfer (HLCT) characteristics, and good thermal stabilities. The C2 series compounds, PPIM-22F, PPIM-23F, and PPIM-2CN, all show redder emission peaks than the N1 series counterparts of PPIM-12F, PPIM-13F, and PPIM-1CN. In addition, the LUMO energy levels decrease consecutively in the sequence of PPIM-22F < PPIM-23F < PPIM-2CN and are all lower than their respective N1 series position isomers of PPIM-12F, PPIM-13F, and PPIM-1CN. The CV measurements indicate that such a design strategy renders the fine-tuning of LUMO energy levels, and the incorporation of electron acceptors at the extended C2 position of the PI unit is a better choice to improve the electron injection ability. Theoretical simulations indicate that they may harvest the triplet exciton through an upper-level reverse intersystem crossing process, which decreases the gathering of triplet excitons and allows the OLEDs to be fabricated by nondoping technology. Among them, PPIM-22F with a difluorobenzene substituent at the C2 position manifests the best performance in OLEDs, which exhibits the maximum EQE of 7.87% and Commission Internationale de lEclairage (CIE) coordinates of (0.16, 0.10). This work demonstrates an effective strategy for considerable improvement in device performance by a subtle change in the molecular structure through isomer engineering.

Room-Temperature Two-Dimensional InSe Plasmonic Laser.

Two-dimensional (2D) semiconductors, owing to their strong excitonic emission, are emerging as efficient gain media for constructing the ultimate nanolaser. The further integration of 2D semiconductors with plasmonic devices holds promise for realizing the thinnest laser. However, the implementation of 2D semiconductor plasmonic lasing is severely hindered by the limited cavity feedback and low gain resulting from insufficient plasmon-exciton interactions. Here, we report the realization of a room-temperature 2D semiconductor plasmonic laser by embedding an InSe nanoflake into a plasmonic Fabry-Perot (F-P) cavity. This plasmonic F-P cavity shows an exceptional ability to recycle the leaked dark surface plasmon, resulting in >2-fold enhancement of feedback compared to that of conventional metal-insulator-semiconductor nanolasers. Moreover, via combination of field enhancement and orientation matching, this cavity facilitates optimized plasmon-exciton coupling to ensure sufficient gain for sustaining room-temperature lasing. Our work may open up the possibilities for multifunctional photonic devices based on 2D materials.

Giant Optical Anisotropy Induced by Magnetic Order in FePS3/WSe2 Heterostructures.

Magnetic 2D materials offer a promising platform for manipulating quantum states at the nanoscale. Recent studies have underscored the significant influence of 2D magnetic materials on the optical behaviors of transition-metal dichalcogenides (TMDs), revealing phenomena such as interlayer exciton-magnon interactions, magnetization-dependent valley polarization, and an enhanced Zeeman effect. However, the controlled manipulation of anisotropic optical properties in TMDs via magnetism remains challenging. Here, the magnetic ordering in FePS3 profoundly impacts the optical characteristics of WSe2, achieving a giant linear polarization degree of 5.1 in exciton emission is demonstrated. This is supported by a detailed analysis of low-temperature photoluminescence (PL) and Raman spectra from nL-FePS3/WSe2 heterostructures. These findings indicate that a phase transition in FePS3 from paramagnetic to antiferromagnetic enhances interlayer Coulomb interactions, inducing a transition from non-polar to polar behavior in the heterostructures. Additionally, valley-polarized PL spectra under magnetic fields from -9 to 9 T reveal the influence of FePS3 on valley polarization and Zeeman splitting of excitons in monolayer WSe2. These results present a novel strategy for tailoring the optoelectronic properties of 2D magnetic van der Waals heterostructures, paving the way for advancements in nanoscale device design.

High-Temperature Excitonic Condensation in 2D Lattice.

Exploration of high-temperature bosonic condensation is of significant importance for the fundamental many-body physics and applications in nanodevices, which, however, remains a huge challenge. Here, in combination of many-body perturbation theory and first-principles calculations, a new-type spatially indirect exciton can be optically generated in two-dimensional (2D) Bi2S2Te because of its unique structure feature. In particular, the spin-singlet spatially indirect excitons in Bi2S2Te monolayer are dipole/parity allowed and reveal befitting characteristics for excitonic condensation, such as small effective mass and satisfied dilute limitation. Based on the layered Bi2S2Te, the possibility of the high-temperature excitonic Bose-Einstein condensation (BEC) and superfluid state in two dimensions, which goes beyond the current paradigms in both experiment and theory, are proved. It should be highlighted that record-high phase transition temperatures of 289.7 and 72.4 K can be theoretically predicted for the excitonic BEC and superfluidity in the atomic thin Bi2S2Te, respectively. It therefore can be confirmed that Bi2S2Te featuring bound bosonic states is a fascinating 2D platform for exploring the high-temperature excitonic condensation and applications in such as quantum computing and dissipationless nanodevices.

Mechanism of Pressure-Modulated Self-Trapped Exciton Emission in Cs2TeCl6 Double Perovskite.

Pressure-modulated self-trapped exciton (STE) emission mechanism in all-inorganic lead-free metal halide double perovskites characterized by large Stokes-shifted broadband emission, has attracted much attention across various fields such as optics, optoelectronics, and biomedical sciences. Here, by employing the all-inorganic lead-free metal halide double perovskite Cs2TeCl6 as a paradigm, the authors elucidate that the performance of STE emission can be modulated by pressure, attributable to the pressure-induced evolution of the electronic state (ES). Two ES transitions happen at pressures of 1.6 and 5.8 GPa, sequentially. The electronic behaviors of Cs2TeCl6 can be jointly modulated by both pressure and ES transitions. When the pressure reaches 1.6 GPa, the Huang-Rhys factor S, indicative of the strength of electron-phonon coupling, attains an optimum value of ≈12.0, correlating with the pressure-induced photoluminescence (PL) intensity of Cs2TeCl6 is 4.8-fold that of its PL intensity under ambient pressure. Through analyzing the pressure-dependent STE dynamic behavioral changes, the authors have revealed the microphysical mechanism underlying the pressure-modulated enhancement and quenching of STE emission in Cs2TeCl6.

Cavity-Tuned Exciton Dynamics in Transition Metal Dichalcogenides Monolayers.

A fully quantum, numerically accurate methodology is presented for the simulation of the exciton dynamics and time-resolved fluorescence of cavity-tuned two-dimensional (2D) materials at finite temperatures. This approach was specifically applied to a monolayer WSe2 system. Our methodology enabled us to identify the dynamical and spectroscopic signatures of polaronic and polaritonic effects and to elucidate their characteristic timescales across a range of exciton-cavity couplings. The approach employed can be extended to simulation of various cavity-tuned 2D materials, specifically for exploring finite temperature nonlinear spectroscopic signals.

Two-Dimensional Exciton Oriented Diffusion via Periodic Potentials.

Excitonic devices operate based on excitons, which can be excited by photons as well as emitting photons and serve as a medium for photon-carrier conversion. Excitonic devices are expected to combine the advantages of both the high response rate of photonic devices and the high integration of electronic devices simultaneously. However, because of the neutral feature, exciton transport is generally achieved via diffusion rather than using electric fields, and the efficient control of exciton flux directionality has always been difficult. In this work, a precisely designed one-dimensional periodic nanostructure (1DPS) is used to introduce periodic strain field along with resonant mode to the WS2 monolayer, achieving exciton oriented diffusion with a 7.6-fold exciton diffusion coefficient enhancement relative to that of intrinsic, while enhancing the excitonic emission intensity by a factor of 10 and reducing exciton saturation threshold power by 2 orders of magnitude. Based on the analysis of the density functional theory (DFT) and the finite-element method (FEM), we attribute the anisotropy of exciton diffusion to exciton funneling induced by periodic potentials, which do not require excessive potential height difference for an efficient oriented diffusion. As a result of resonant emission, the exciton diffusion is dragged into the nonlinear regime owing to the high exciton density close to saturation, which improves the exciton diffusion coefficient and diffusion anisotropy more appreciably.