Control of Hybrid Exciton Lifetime in MoSe2/WS2 Moiré Heterostructures.

Hybrid excitons, characterized by their strong oscillation strength and long lifetimes, hold great potential as information carriers in semiconductors. They offer promising applications in exciton-based devices and circuits. MoSe2/WS2 heterostructures represent an ideal platform for studying hybrid excitons, but how to regulate the exciton lifetime has not yet been explored. In this study, layer hybridization is modulated by applying electric fields parallel or antiparallel to the dipole moment, enabling us to regulate the exciton lifetime from 1.36 to 4.60 ns. Furthermore, the time-resolved photoluminescence decay traces are measured at different excitation power. A hybrid exciton annihilation rate of 8.9 × 10-4 cm2 s-1 is obtained by fitting. This work reveals the effects of electric fields and excitation power on the lifetime of hybrid excitons in MoSe2/WS2 1.5° moiré heterostructures, which play important roles in high photoluminescence quantum yield optoelectronic devices based on transition-metal dichalcogenides heterostructures.

Out-of-Plane Ferroelectricity in Two-Dimensional 1T‴-MoS2 Above Room Temperature.

Two-dimensional (2D) molybdenum disulfide (MoS2), one of the most extensively studied van der Waals (vdW) materials, is a significant candidate for electronic materials in the post-Moore era. MoS2 exhibits various phases, among which the 1T‴ phase possesses noncentrosymmetry. 1T‴-MoS2 was theoretically predicted to be ferroelectric a decade ago, but this has not been experimentally confirmed until now. Here, we have prepared high-purity 2D 1T‴-MoS2 crystals and experimentally confirmed the room-temperature out-of-plane ferroelectricity. The noncentrosymmetric crystal structure in 2D 1T‴-MoS2 was convinced by atomically resolved transmission electron microscopic imaging and second harmonic generation (SHG) measurements. Further, the ferroelectric polarization states in 2D 1T‴-MoS2 can be switched using piezoresponse force microscopy (PFM) and electrical gating in field-effect transistors (FETs). The ferroelectric-to-paraelectric transition temperature is measured to be about 350 K. Theoretical calculations have revealed that the ferroelectricity of 2D 1T‴-MoS2 originates from the intralayer charge transfer of S atoms within the layer. The discovery of intrinsic ferroelectricity in the 1T‴ phase of MoS2 further enriches the properties of this important vdW material, providing more possibilities for its application in the field of next-generation electronic devices.

Direct Visualization of Dark Interlayer Exciton Transport in Moiré Superlattices.

Moiré superlattices have emerged as an unprecedented manipulation tool for engineering correlated quantum phenomena in van der Waals heterostructures. With moiré potentials as a naturally configurable solid-state that sustains high exciton density, interlayer excitons in transition metal dichalcogenide heterostructures are expected to achieve high-temperature exciton condensation. However, the exciton degeneracy state is usually optically inactive due to the finite momentum of interlayer excitons. Experimental observation of dark interlayer excitons in moiré potentials remains challenging. Here we directly visualize the dark interlayer exciton transport in WS2/h-BN/WSe2 heterostructures using femtosecond transient absorption microscopy. We observe a transition from classical free exciton gas to quantum degeneracy by imaging temperature-dependent exciton transport. Below a critical degeneracy temperature, exciton diffusion rates exhibit an accelerating downward trend, which can be explained well by a nonlinear quantum diffusion model. These results open the door to quantum information processing and high-precision metrology in moiré superlattices.

Non-contact friction energy dissipation via hysteretic behavior on a graphite surface.

For non-contact friction, energy is usually dissipated through phonon excitation, Joule dissipation and van der Waals friction. Although some new dissipation mechanisms related to the quantum phenomenon have been discovered, the contribution of hysteretic behavior to non-contact friction energy dissipation is lacking in research. In this paper, the distance dependence of non-contact friction on the graphite surface is studied by using a quartz tuning fork with lateral vibration in the atmosphere. It is found that energy dissipation begins to increase when the distance is less than 2 nm, showing the form of phonon dissipation. However, when the distance is further decreased, the dissipation deviates from phonon dissipation and presents a huge friction energy dissipation peak, which is caused by the hysteretic behavior between the vibration of the surface atoms and the oscillation of the tip. This work expands the understanding of the energy dissipation mechanism of non-contact friction.

Visualizing Ultrafast Defect-Controlled Interlayer Electron-Phonon Coupling in Van der Waals Heterostructures.

Engineering ultrafast interlayer coupling provides access to new quantum phenomena and novel device functionalities in atomically thin van der Waals heterostructures. However, due to all the atoms of a monolayer material being exposed at the interfaces, the interlayer coupling is extremely susceptible to defects, resulting in high energy dissipation through heat and low device performance. The study of how defects affect the interlayer coupling at ultrafast and atomic scales remains a challenge. Here, using femtosecond transient absorption microscopy, a new defect-induced ultrafast interlayer electron-phonon coupling pathway is identified in a WS2 /graphene heterostructure, involving a three-body collision between electrons in WS2 and both acoustic phonons and defects in graphene. This interaction manifests as the reduced defect-related Raman resonant activity and the accelerated electron-phonon scattering time from 7.1 to 2.4 ps. Furthermore, the ultrafast interlayer coupling process is directly imaged. These insights will advance the fundamental knowledge of heat dissipation in nanoscale devices, and enable new ways to dynamically manipulate electrons and phonons via defects in van der Waals heterostructures.

Twist-angle-controlled neutral exciton annihilation in WS2 homostructures.

Exciton-exciton annihilation (EEA), as typical nonradiative recombination, plays an unpopular role in semiconductors. The nonradiative process significantly reduces the quantum yield of photoluminescence, which substantially inhibits the maximum efficiency of optoelectronic devices. Recently, laser irradiation, introducing defects and applying strain have become effective means to restrain EEA in two-dimensional (2D) transition metal dichalcogenides (TMDCs). However, these methods destroy the atomic structure of 2D materials and limit their practical applications. Fortunately, twisted structures are expected to validly suppress EEA through excellent interface quality. Here, we develop a non-destructive way to control EEA in WS2 homostructures by changing the interlayer twist angle, and systematically study the effect of interlayer twist angle on EEA, using fluorescence lifetime imaging measurement (FLIM) technology. Due to the large moiré potential at a small interlayer twist angle, the diffusion of excitons is hindered, and the EEA rate decreases from 1.01 × 10-1 cm2 s-1 in a 9° twisted WS2 homostructure to 4.26 × 10-2 cm2 s-1 in a 1° twisted WS2 homostructure. The results reveal the important role of the interlayer twist angle and EEA interaction in high photoluminescence quantum yield optoelectronic devices based on TMDC homostructures.

Imaging of Defect-Accelerated Energy Transfer in MoS2/hBN/WS2 Heterostructures.

Engineering energy transfer (ET) plays an important role in the exploration of novel optoelectronic devices. The efficient ET has been reasonably regulated using different strategies, such as dielectric properties, distance, and stacking angle. However, these strategies show limited degrees of freedom in regulation. Defects can provide more degrees of freedom, such as the type and density of defects. Herein, atomic-scale defect-accelerated ET is directly observed in MoS2/hBN/WS2 heterostructures by fluorescence lifetime imaging microscopy. Sulfur vacancies with different densities are introduced by controlling the oxygen plasma irradiation time. Our study shows that the ET rate can be increased from 1.25 to 6.58 ns-1 by accurately controlling the defect density. Also, the corresponding ET time is shortened from 0.80 to 0.15 ns, attributing to the participation of more neutral excitons in the ET process. These neutral excitons are transformed from trion excitons in MoS2, assisted by oxygen substitution at sulfur vacancies. Our insights not only help us better understand the role of defects in the ET process but also provide a new approach to engineer ET for further exploration of novel optoelectronic devices in van der Waals heterostructures.

In situ Plasmon-Enhanced CARS and TPEF for Gram staining identification of non-fluorescent bacteria.

In this work, we report in situ nonlinear microscopic images on plasmon-enhanced coherent anti-Stokes Raman scattering (CARS) and plasmon-Induced two-photon excited fluorescence （TPEF)of non-fluorescent microorganism. Our unique synthesized Au@Ag nanorods provide with two distinct surface-plasmon resonance (SPR) at 400 and 800 nm, respectively, which can efficiently induce linear fluorescence signals of E. coli but also enhance the nonlinear optical spectroscopy signals of TPEF, and coherent anti-Stokes Raman scattering (CARS) imaging of E. coli and S. aureus. Furthermore, calculations with complete active space self-consistent field (CASSCF) reveals the hot electrons of SPs can efficiently induce the biological fluorescence of non-fluorescent flavin nucleotides on the surface of E. coli. This novel mechanism is expected to guide the development and application of new microbial detection reagents. Gram-negative and Gram-positive bacteria can be well distinguished by nonlinear microscopic imaging of the CARS signal at 1589 cm-1. Benefit by the strong penetrability of non-linear optical signals, it is expected to realize in situ real-time detection and classification of pathogenic microbial infections in vivo.

Physical mechanism of concentration-dependent fluorescence resonance energy transfer.

We experimentally report fluorescence resonance energy transfer (FRET), using a novel visualization method of excitation-emission mapping. Firstly, both the absorption and fluorescent spectra of donor and acceptor are measured, respectively, under different molecular concentrations for verifying that these two molecules are suitable for exploring FRET. And then, the excitation-emission mappings of FRET are investigated to reveal the internal regular pattern of FRET. Our theoretical calculations strongly support experimental results of FRET. Our experimental results provided a new visualization method to clearly understand the mechanism of FRET.

Ultrasensitive SERS detection of rhodamine 6G and p-nitrophenol based on electrochemically roughened nano-Au film.

Quantitative analysis of organic pollutants in environmental water is an important issue for ecological environment and human health. In this paper, the quantitative analysis of rhodamine 6G (R6G) and p-nitrophenol (PNP) is performed by the surface enhanced Raman scattering (SERS) technology. The enhancement of Raman signals is achieved on the surface of an electrochemically roughened nano-Au film. The SERS performance depends on the microstructure of roughened nano-Au films, which is affected by the thickness of Au films and electrochemical roughening parameters. The structure-dependence of SERS performance is validated by finite element simulation of local electromagnetic field distribution. An obvious SERS effect of R6G with an enhancement factor of 108 is obtained on the roughened nano-Au film. A sensitive SERS detection of R6G with a linear range of 10-9-10-5 M and a detection limit of 10-11 M is realized. Moreover, a wide linear range of 10-9-10-3 M is obtained for the detection of PNP. The roughened nano-Au film is an effective substrate for the SERS detection of organic pollutants with high reproducibility and good stability. Therefore, the electrochemical technology in this study is expected to be a very promising method for the fabrication of high-performance SERS substrate.

Raman spectroscopy as a potential diagnostic tool to analyse biochemical alterations in lung cancer.

Patient survival remains poor even after diagnosis in lung cancer cases, and the molecular events resulting from lung cancer progression remain unclear. Raman spectroscopy could be used to noninvasively and accurately reveal the biochemical properties of biological tissues on the basis of their pathological status. This study aimed at probing biomolecular changes in lung cancer, using Raman spectroscopy as a potential diagnostic tool. Herein, biochemical alterations were evident in the Raman spectra (region of 600-1800 cm-1) in normal and cancerous lung tissues. The levels of saturated and unsaturated lipids and the protein-to-lipid, nucleic acid-to-lipid, and protein-to-nucleic acid ratios were significantly altered among malignant tissues compared to normal lung tissues. These biochemical alterations in tissues during neoplastic transformation have profound implications in not only the biochemical landscape of lung cancer progression but also cytopathological classification. Based on this spectroscopic approach, classification methods including k-nearest neighbour (kNN) and support vector machine (SVM) were successfully applied to cytopathologically diagnose lung cancer with an accuracy approaching 99%. The present results indicate that Raman spectroscopy is an excellent tool to biochemically interrogate and diagnose lung cancer.

The nature of photoinduced intermolecular charger transfer in fluorescence resonance energy transfer.

In this paper, we report time resolved fluorescence resonance energy transfer (FRET) using femtosecond ultrafast transient absorption spectroscopy. The lifetimes of FRET are strongly dependent on the molecular concentration and ratio of donor and acceptor. Also, in the FRET, photoinduced intermolecular charge transfer (PICT) is also investigated theoretically. The driving force for PICT in FRET system equals the reorganization energy, which gives barrier-less charge transfer according to Marcus theory. The rates of PICT in the FRET system can be estimated with our simplified Marcus equation. Our results of PICT in FRET system provide a new efficient way for the charge transfer in donor-acceptor system.

Physical mechanism of photoinduced intermolecular charge transfer enhanced by fluorescence resonance energy transfer.

In this paper, photoinduced intermolecular charge transfer (PICT) and fluorescence resonance energy transfer (FRET) in donor-acceptor systems have been investigated experimentally and theoretically. We attempt to investigate the natural relationship between FRET and PICT, and reveal the advantages of FRET enhanced PICT. The driving force for PICT in the FRET system equals the reorganization energy, which gives barrier-less charge transfer according to Marcus theory. The rates of PICT in the FRET system can be estimated with our simplified Marcus equation. Our results can promote the deeper understanding of the nature of FRET enhanced PICT, and benefit rational design for the use of the FRET system in organic solar cells.

Surface Plasmon Resonance Sensors on Raman and Fluorescence Spectroscopy.

The performance of chemical reactions has been enhanced immensely with surface plasmon resonance (SPR)-based sensors. In this review, the principle and application of SPR sensors are introduced and summarized thoroughly. We introduce the mechanism of the SPR sensors and present a thorough summary about the optical design, including the substrate and excitation modes of the surface plasmons. Additionally, the applications based on SPR sensors are described by the Raman and fluorescence spectroscopy in plasmon-driven surface catalytic reactions and the measurement of refractive index sensing, especially.