Trion Emission Research Articles

Excitonic performance and ultrafast dynamics in defective WSe2

Understanding and facilitating defects in two-dimensional transition metal dichalcogenides (TMDCs) are of fundamental importance for their application in optoelectronic devices and valleytronic devices. In this study, swift heavy ion (SHI) irradiation was applied to introduce defects in monolayer WSe2 in a controlled manner. Temperature-dependent photoluminescence and transient absorption spectroscopy are employed to investigate the excitonic performances in defective WSe2. It is observed that the trion emission rises up alongside exciton emission for WSe2 irradiated with elevated ion fluences. Defects introduced by SHI irradiation can strongly localize carriers and weaken the exciton–phonon coupling and further affect the optical signatures of the excitons. Photoexcited electron–hole pairs were suppressed to form excitons due to the weaken phonon scattering, and the population of exciton was reduced for the irradiated WSe2. These results reveal that SHI irradiation is an effective technique to explore defect dependence of exciton formation and evolution dynamics in TMDCs, which have important implications for various optoelectronic applications.

Trion-trion annihilation in monolayer WS2

Strong Coulomb interaction in monolayer transition metal dichalcogenides can facilitate nontrivial many-body effects among excitonic complexes. Many-body effects like exciton-exciton annihilation (EEA) have been widely explored in this material system. However, a similar effect for charged excitons (or trions), that is, trion-trion annihilation (TTA), is expected to be relatively suppressed due to repulsive like-charges, and has not been hitherto observed in such layered semiconductors. By a gate-dependent tuning of the spectral overlap between the trion and the charged biexciton through an "anti-crossing"-like behaviour in monolayer WS$_2$, here we present an experimental observation of an anomalous suppression of the trion emission intensity with an increase in gate voltage. The results strongly correlate with time-resolved measurements, and are inferred as a direct evidence of a nontrivial TTA resulting from non-radiative Auger recombination of a bright trion, and the corresponding energy resonantly promoting a dark trion to a charged biexciton state. The extracted Auger coefficient for the process is found to be tunable ten-fold through a gate-dependent tuning of the spectral overlap.

Simultaneous control of plasmon–exciton and plasmon–trion couplings in an Au nanosphere and monolayer WS2 hybrid system

Simultaneous control of plasmon–exciton and plasmon–trion couplings is fundamentally interesting for tailoring the strong light–matter interaction at the nanoscale and is intriguing for developing high-efficiency optoelectronic and nonlinear photonic devices. Here, we integrate the monolayer WS2 with the Au nanosphere to take full advantages of both the strong excitonic effect and local field enhancement effect to realize strong resonance couplings between the dipolar plasmon mode and the exciton, as well as the trion, at room temperature. Interestingly, from the dark-field scattering spectrum, a transition from the dominated plasmon–exciton coupling to the plasmon–exciton–trion coupling in the hybrid system by simply increasing the radius of the nanosphere is revealed. This evolution of the scattering spectrum is further analyzed using the coupled-oscillator model to extract Rabi splittings of 89 and 48 meV for plasmon–exciton and plasmon–trion couplings, implying that the hybrid system enters the moderate coupling region. The moderate coupling imparts the hybrid system with a remarkable light-emitting capacity, rendering 1265- and 680-fold photoluminescence (PL) enhancement for the exciton and trion emissions, respectively. Our findings provide a facile way for the manipulation of excitonic quasiparticles in semiconductors at room temperature.

Revealing the impact of strain in the optical properties of bubbles in monolayer MoSe2.

Strain plays an important role for the optical properties of monolayer transition metal dichalcogenides (TMDCs). Here, we investigate strain effects in a monolayer MoSe2 sample with a large bubble region using μ-Raman, second harmonic generation (SHG), μ-photoluminescence and magneto μ-photoluminescence at low temperature. Remarkably, our results reveal the presence of a non-uniform strain field and the observation of emission peaks at lower energies which are the signatures of exciton and trion quasiparticles red-shifted by strain effects in the bubble region, in agreement with our theoretical predictions. Furthermore, we have observed that the emission in the strained region decreases the trion binding energy and enhances the valley g-factors as compared to non-strained regions. Considering uniform biaxial strain effects within the unit cell of the TMDC monolayer (ML), our first principles calculations predict the observed enhancement of the exciton valley Zeeman effect. In addition, our results suggest that the exciton-trion fine structure plays an important role for the optical properties of strained TMDC ML. In summary, our study provides fundamental insights on the behaviour of excitons and trions in strained monolayer MoSe2 which are particularly relevant to properly characterize and understand the fine structure of excitonic complexes in strained TMDC systems/devices.

Spin dependent charge transfer in MoSe2/hBN/Ni hybrid structures

We present magneto-photoluminescence measurements in a hybrid two-dimensional semiconductor/ferromagnetic structure consisting of MoSe2/hBN/Ni. When the nickel layer is magnetized, we observe circularly polarized photoluminescence of the trion peak in the MoSe2 monolayer under linearly polarized excitation. This build-up of circular polarization can reach a measured value of about 4% when the magnetization of Ni is saturated perpendicularly to the sample plane and changes its sign when the magnetization is reversed. The circular polarization decreases when the hBN barrier thickness increases. These results are interpreted in terms of a spin-dependent charge transfer between the MoSe2 monolayer and the nickel film. The build-up of circular polarization is observed up to 120 K, mainly limited by the trion emission that vanishes with temperature.

The influence of temperature of nitridation and AlN buffer layer on N-polar GaN

The influence of temperature of nitridation and AlN buffer layer growth on N-polar gallium nitride (GaN) grown on 2-in. vicinal sapphire substrate by metal organic chemical vapour deposition (MOCVD) is investigated in this study. A medium temperature (1000 °C) leads to a relatively rougher surface but improved crystalline quality, enhanced optical performance, and higher electron mobility. The relatively stronger yellow luminescence and weaker near-band-edge (NBE) emission of the N-polar GaN undergoing a high temperature (1110 °C) nitridation and AlN buffer layer growth may be attributed to the increase of gallium vacancies, which is further confirmed by the relatively lower electron concentration. The sublinear excitation power dependence of the NBE emission may refer to the trion emission formed by the defect-bounded excitons.

Nanoscale Modification of WS2 Trion Emission by Its Local Electromagnetic Environment

Structural, electronic, and chemical nanoscale modifications of transition metal dichalcogenide monolayers alter their optical properties. A key missing element for complete control is a direct spatial correlation of optical response to nanoscale modifications due to the large gap in spatial resolution between optical spectroscopy and nanometer-resolved techniques. Here, we bridge this gap by obtaining nanometer-resolved optical properties using electron spectroscopy at cryogenic temperatures, specifically electron energy loss spectroscopy for absorption and cathodoluminescence for emission, which are then directly correlated to chemical and structural information. In an h-BN/WS2/h-BN heterostructure, we observe local modulation of the trion (X-) emission due to tens of nanometer wide dielectric patches. Trion emission also increases in regions where charge accumulation occurs, close to the carbon film supporting the heterostructures. The localized exciton emission (L) detected here is not correlated to strain above 1%, suggesting point defects might be involved in their formation.

Origin of Low Temperature Trion Emission in CdSe Nanoplatelets.

Colloidal semiconductor nanoplatelets (NPLs) are a scalable materials platform for optoelectronic applications requiring fast and narrow emission, including spin-to-photon transduction within quantum information networks. In particular, three-particle negative trions of NPLs are appealing emitters since, unlike excitons, they do not have an optically "dark" sublevel. In CdSe NPLs, trion emission dominates the photoluminescence (PL) spectrum at low temperature but using them as single photon-emitting states requires more knowledge about their preparation, since trions in these materials are not directly optically accessible from the ground state. This work demonstrates, using power-dependent time-resolved transient absorptions (TA) of CdSe NPLs, that trions form via biexciton decay in 1.6 ps. The scaling of the trion population and formation lifetime with excitation power indicates that they do not form through collisional mechanisms typical for 2D materials, but rather by a unimolecular hole transfer. This work is a step toward deterministic single photon emission from trions.

Long-Range Directional Routing and Spatial Selection of High-Spin-Purity Valley Trion Emission in Monolayer WS2.

Valley-dependent excitation and emission in transition metal dichalcogenides (TMDCs) have recently emerged as a new avenue for optical data manipulation, quantum optical technologies, and chiral photonics. The valley-polarized electronic states can be optically addressed through photonic spin-orbit interaction of excitonic emission, typically with plasmonic nanostructures, but their performance is limited by the low quantum yield of neutral excitons in TMDC multilayers and the large Ohmic loss of plasmonic systems. Here, we demonstrate a valleytronic system based on the trion emission in high-quantum-yield WS2 monolayers chirally coupled to a low-loss microfiber. The integrated system uses the spin properties of the waveguided modes to achieve long-range directional routing of valley excitations and also provides an approach to selectively address valley-dependent emission from different spatial locations around the microfiber. This valleytronic interface can be integrated with fiber communication devices, allowing for merging valley polarization and chiral photonics as an alternative mechanism for optical information transport and manipulation in classical and quantum regimes.

Imaging Charged Exciton Localization in van der Waals WSe2/MoSe2 Heterobilayers.

Exciton localization in transition-metal dichalcogenide monolayers is behind a variety of interesting phenomena and applications, including broad-spectrum solar cells and single-photon emissions. Strain fields at the periphery of topographically distinct features such as nanoscopic bubbles were recently associated with localized charge-neutral excitons. Here, we use tip-enhanced photoluminescence (PL) to visualize excitons in WSe2/MoSe2 heterobilayers (HBL). We find strong optical emission from charged excitons, particularly positively charged trions, in HBL supported by interlayer charge transfer. Our results reveal strong trion confinement, with a localization length scale comparable to the trion size, at the apex region inside individual nanoscopic bubbles. Nano-PL mapping also shows sub-10-nm spatial variations in the localized trion emission spectra, which stem from atomic-scale potential energy fluctuations. These findings demonstrate the possibility of confining charged exciton complexes that are electrically tunable, opening up further opportunities to probe many-body exciton physics and to explore additional possible sites for strong exciton localization that can lead to quantum emission.

Investigation of carrier migration from WS2 monolayer to substrate by photoluminescence

Carriers in atomically thin two-dimensional (2D) semiconductors like WS2 monolayers are prone to interact with their surroundings, which may have a significant impact on both the electric and optical properties of 2D semiconductors. In this work, abnormal dependence of photoluminescence (PL) intensity on excitation power densities is observed in mechanically exfoliated WS2 monolayers on SiO2/Si substrates, which is manifested as a sudden intensity drop of exciton and trion emissions at certain power density followed by much slowed intensity increase. As-exfoliated and wetted WS2 monolayers exhibit similar abnormal variation of PL intensity but different power densities that trigger the intensity drop. The sudden drop of PL intensity is ascribed to the modification to the contact status of the monolayer with the substrate, caused by the interplay of the trapped air or water with the monolayer and the substrate upon laser irradiation, which therefore alters the carries transport rate from the monolayer to the substrate. A rate equation model has been developed to delicately deal with the carrier recombination and transport processes in a steady state, and the variation dependence of exciton, trion and free charge populations on the cross-plane transport rate is demonstrated, which consistently explains the abnormal PL intensity dependence on the excitation power density. The important role of carrier transport in the PL performance has been verified in this work, and further understanding of the carrier interactions in atomical thin 2D semiconductors has been achieved.

Influence of direct deposition of dielectric materials on the optical response of monolayer WS2

We investigate the effects of direct deposition of different dielectric materials (AlOx, SiOx, SiNx) onto atomically thin TMDC WS2 on its optical response using atomic layer deposition (ALD), electron beam evaporation (EBE), plasma-enhanced chemical vapor deposition (PECVD), and magnetron sputtering. The photoluminescence measurements reveal quenching of the excitonic emission after all deposition processes, which is linked to the increased level of charge doping and associated rise of the trion emission and/or the localized (bound) exciton emission. Furthermore, Raman spectroscopy allows us to clearly correlate the observed changes in excitonic emission with the increased levels of lattice disorder and defects. In particular, we show that the different doping levels in a monolayer WS2 capped by a dielectric material are strongly related to the defects in the WS2 crystal introduced by all capping methods, except for ALD. The strong charge doping in the ALD-capped sample seems to be caused by other factors, such as deviations in the dielectric layer stoichiometry or chemical reactions on the monolayer surface, which makes ALD distinct from all other techniques. Overall, the EBE process results in the lowest level of doping and defect densities and in the largest spectral weight of the exciton emission in the PL. Sputtering is revealed as the most aggressive dielectric capping method for WS2, fully quenching its optical response. Our results demonstrate and quantify the effects of direct deposition of dielectric materials onto monolayer WS2, which can provide valuable guidance for the efforts to integrate monolayer TMDCs into functional optoelectronic devices.

Optical read-out of Coulomb staircases in a moir\xe9 superlattice via trapped interlayer trions

Moiré patterns with a superlattice potential can be formed by vertically stacking two layered materials with a relative twist or lattice constant mismatch. In transition metal dichalcogenide-based systems, the moiré potential landscape can trap interlayer excitons (IXs) at specific atomic registries. Here, we report that spatially isolated trapped IXs in a molybdenum diselenide/tungsten diselenide heterobilayer device provide a sensitive optical probe of carrier filling in their immediate environment. By mapping the spatial positions of individual trapped IXs, we are able to spectrally track the emitters as the moiré lattice is filled with excess carriers. Upon initial doping of the heterobilayer, neutral trapped IXs form charged IXs (IX trions) uniformly with a binding energy of ~7 meV. Upon further doping, the empty superlattice sites sequentially fill, creating a Coulomb staircase: stepwise changes in the IX trion emission energy due to Coulomb interactions with carriers at nearest-neighbour moiré sites. This non-invasive, highly local technique can complement transport and non-local optical sensing techniques to characterize Coulomb interaction energies, visualize charge correlated states, or probe local disorder in a moiré superlattice.

Exciton Transitions in Monolayer WS2 Activated by Swift Heavy Ion Irradiation

The emergence of monolayer transition metal dichalcogenides (TMDCs) has provided a favorable platform for exploring a broad range of novel optoelectronic device applications and quantum phenomena due to their remarkable physical and chemical characteristics. Understanding the transition and motion of excitons in TMDCs is of fundamental interest for their optoelectronic devices. Here, we demonstrate the exciton transition in monolayer WS2 that can be fine-tuned by swift heavy ion (SHI) irradiation. The dependence of trion and exciton emissions on SHI irradiation in the as-transferred and as-grown monolayer WS2 was investigated by micro photoluminescence (PL) spectra where different PL responses were monitored. The trion-to-exciton transition in the as-transferred WS2 monolayer was ascribed to SHI irradiation that resulted in charge localization and pre-existing defect annealing, whereas the exciton-to-trion transition in the as-grown WS2 monolayer was attributed to the competition of charge localization and charge transfer caused by SHI irradiation. Femtosecond transient absorption measurements were performed to study the exciton relaxation dynamics in SHI-irradiated WS2, and it was shown that defect-assisted recombination dominates the exciton relaxation process for SHI-irradiated WS2. These results open up new opportunities to manipulate and tune the optical properties of two-dimensional TMDCs, which are of special importance for the development of optoelectronic and valleytronic devices.

Hexagram bi-layer MoS2 flake: The impact of polycrystallinity and strains on the exciton and trion photoluminescence

Atomically-thin MoS2 is a favorable material for flexible device and nano-optoelectronics application due to unique optical and photoelectrical properties related to the exciton and trion formation. These properties crucially depend on the flake structure, strains and surrounding environment. MoS2 flakes of hexagram (six-pointed star) shape grown by CVD on SiO2/Si are known to be polycrystalline, consisting of six rhomb-like single-crystals with grain boundaries and having uneven residual tensile strains. So, it is an attractive object for studying the influence of polycrystallinity and strains on the exciton and trion emission behavior. In this paper, the micro-photoluminescence (µ-PL) of a bi-layer MoS2 flake of hexagram shape is studied in comparison with a triangular flake of the same thickness and a similar size. The morphology, structural and optical properties are inspected, focusing on the impact of the flake polycrystallinity and residual tensile strains on the exciton and trion PL. It is shown that the hexagram flake possesses special spectral features: an increased exciton PL intensity and the band peak energy shifted towards higher energy at the boundaries between the constituent single-crystals. In contrast, the triangular flake demonstrates rather even spatial distribution of PL. The spectral differences between both the flakes and their parts are explained in terms of tensile strains appearing in MoS2 on SiO2/Si after the post-growth cooling. The tensile strains are shown to redshift all the spectral bands and reduce the A exciton contribution to the spectrum, thus increasing the spectral weight of the B exciton and trion bands.

Observation of Diffusion and Drift of the Negative Trions in Monolayer WS2.

Monolayer transition metal dichalcogenides (ML-TMDCs) are a versatile platform to explore the transport dynamics of the tightly bound excitonic states. The diffusion of neutral excitons in various ML-TMDCs has been observed. However, the transport of charged excitons (trions), which can be driven by an in-plane electric field and facilitate the formation of an excitonic current, has yet been well investigated. Here, we report the direct observation of diffusion and drift of the trions in ML-WS2 through spatially and time-resolved photoluminescence. An effective diffusion coefficient of 0.47 cm2/s was extracted from the broadening of spatial profiles of the trion emission. When an in-plane electric field is applied, the spatial shift of the trion emission profiles indicated a drift velocity of 7400 cm/s. Both the diffusion caused broadening and the drift caused shift of the emission profiles saturate because of the Coulomb interactions between trions and the background charges.

Enhanced Trion Emission in Monolayer MoSe2 by Constructing a Type‐I Van Der Waals Heterostructure

AbstractTrions, quasi‐particles consisting of two electrons combined with one hole or of two holes with one electron, have recently been observed in transition metal dichalcogenides (TMDCs) and drawn increasing attention due to potential applications of these materials in light‐emitting diodes, valleytronic devices as well as for being a testbed for understanding many‐body phenomena. Therefore, it is important to enhance the trion emission and its stability. In this study, a MoSe2/FePS3 van der Waals heterostructure (vdWH) with type‐I band alignment is constructed, which allows for carriers injection from FePS3 to MoSe2. At low temperatures, the neutral exciton (X0) emission in this vdWH is almost completely suppressed. The ITrion/Ix0 intensity ratio increases from 0.44 in a single MoSe2 monolayer to 20 in this heterostructure with the trion charging state changing from negative in the monolayer to positive in the heterostructure. The optical pumping with circularly polarized light shows a 14% polarization for the trion emission in MoSe2/FePS3. Moreover, forming such type‐I vdWH also gives rise to a 20‐fold enhancement of the room temperature photoluminescence from monolayer MoSe2. These results demonstrate a novel approach to convert excitons to trions in monolayer 2D TMDCs via interlayer doping effect using type‐I band alignment in vdWH.

Light Absorption and Emission Dominated by Trions in the Type-I van der Waals Heterostructures

van der Waals (vdW) heterostructures provide a powerful method to control the alignment of energy bands of atomically thin 2D materials. Under light illumination, the optical responses are dominated by Coulomb-bound electron–hole quasiparticles, for example, excitons, trions, and biexcitons, whose contributions accordingly depend on the types of heterostructures. For type-II heterostructures, it has been well established that light excitation results in electrons and holes that are separated in different layers, and the radiative recombination is dominated by the interlayer excitons. On the contrary, little is known about the corresponding optical responses of type-I cases. Understanding the optical characteristics of type-I heterostructures is important to the full exploration of the quasiparticle physics of the 2D heterostacks. In this study, we performed optical spectroscopy on type-I vdW heterostacks composed of monolayer MoTe2 and WSe2. Photoluminescence and reflection contrast spectroscopy show that the light absorption and emission are dominated by the Coulomb-bound trions. Importantly, we observed that the MoTe2 trion emission gets stronger compared with the exciton emission under resonant light excitation to the WSe2 trion absorption state, especially in the WSe2/MoTe2/WSe2 heterotrilayer. A detailed study of photoluminescence excitation further reveals that the charge-transfer mechanism is likely responsible for our observation, which differs from the exciton-dominated dipole–dipole energy transfer in type-II structures. Our demonstration implies that the type-I vdW heterostack provides new opportunities to engineer the light–matter interactions through many-body Coulomb-bound states.

A High-Efficiency Wavelength-Tunable Monolayer LED with Hybrid Continuous-Pulsed Injection.

High-efficiency and wavelength-tunable light-emitting diode (LED) devices will play an important role in future advanced optoelectronic systems. Traditional semiconductor LED devices typically have a fixed emission wavelength that is determined by the energy of the emission states. Here, a novel high-efficiency and wavelength-tunable monolayer WS2 LED device, which operates in the hybrid mode of continuous-pulsed injection, is developed. This hybrid injection enables highly enhanced emission efficiency (>20 times) and effective size of emission area (>5 times) at room temperature. The emission wavelength of the WS2 monolayer LED device can be tuned over more than 40nm by driving AC voltages, from exciton emission to trion emission, and further to defect emission. The quantum efficiency of defect electroluminescence (EL) emission is measured to be more than 24.5 times larger than that from free exciton and trion EL emission. The separate carrier injection in the LED also demonstrates advantages in allowing defect species to be visualized and distinguished in real space. Those defects are assigned to be negatively charged defects. The results open a new route to develop high-performance and wavelength-tunable LED devices for future advanced optoelectronic applications.

Signatures of moiré trions in WSe2/MoSe2 heterobilayers.

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