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Two-dimensional transition metal dichalcogenides (2D-TMDs) hold a great potential to platform future flexible optoelectronics. The beating hearts of these materials are their excitons known as XA and XB, which arise from transitions between spin-orbit split (SOS) levels in the conduction and valence bands at the K-point. The functionality of 2D-TMD-based devices is determined by the dynamics of these excitons. One of the most consequential channels of exciton decay on the device functionality is the defect-assisted recombination (DAR). Here, we employ steady-state absorption and emission spectroscopies, and pump density-dependent femtosecond transient absorption spectroscopy to report on the effect of DAR on the lifetime of excitons in monolayers of tungsten disulfide (2D-WS2) and diselenide (2D-WSe2). These pump-probe measurements suggested that while exciton decay dynamics in both monolayers are driven by DAR, in 2D-WS2, defect states near the XB exciton fill up before those near the XA exciton. However, in the 2D-WSe2 monolayer, the defect states fill up similarly. Understanding the contribution of DAR on the lifetime of excitons and the partition of this decay channel between XA and XB excitons may open new horizons for the incorporation of 2D-TMD materials in future optoelectronics. 

Interest in layered two-dimensional (2D) materials has been escalating rapidly over the past few decades due to their promising optoelectronic and photonic properties emerging from their atomically thin 2D structural confinements. When these 2D materials are further confined in lateral dimensions toward zero-dimensional (0D) structures, 2D nanoparticles and quantum dots with new properties can be formed. Here, we report a nonequilibrium gas-phase synthesis method for the stoichiometric formation of gallium selenide (GaSe) nanoparticles ensembles that can potentially serve as quantum dots. We show that the laser ablation of a target in an argon background gas condenses the laser-generated plume, resulting in the formation of metastable nanoparticles in the gas phase. The deposition of these nanoparticles onto the substrate results in the formation of nanoparticle ensembles, which are then post-processed to crystallize or sinter the nanoparticles. The effects of background gas pressures, in addition to crystallization/sintering temperatures, are systematically studied. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, and time-correlated single-photon counting (TCSPC) measurements are used to study the correlations between growth parameters, morphology, and optical properties of the fabricated 2D nanoparticle ensembles. 

Excitons in two-dimensional transition metal dichalcogenide monolayers (2D-TMDs) are of essential importance due to their key involvement in 2D-TMD-based applications. For instance, exciton dissociation and exciton radiative recombination are indispensible processes in photovoltaic and light-emitting devices, respectively. These two processes depend drastically on the photogeneration efficiency and lifetime of excitons. Here, we incorporate femtosecond pump–probe spectroscopy to investigate the ultrafast dynamics of exciton formation and decay in a single crystal of monolayer 2D tungsten disulfide (WS 2 ). Investigation of the formation dynamics of the lowest exciton (X A ) indicated that the formation time linearly increases from ∼150 fs upon resonant excitation, to ∼500 fs following excitation that is ∼1.1 eV above the band-gap. This dependence is attributed to the time it takes highly excited electrons in the conduction band (CB) to relax to the CB minimum (CBM) and contribute to the formation of X A . This is confirmed by infrared measurements of electron intraband relaxation dynamics. Furthermore, pump–probe experiments suggested that the X A ground state depletion recovery dynamics depend on the excitation energy as well. The average recovery time increased from ∼10 ps in the case of resonant excitation to ∼50 ps following excitation well above the band-gap. Having the ability to control whether generating short-lived or long-lived electron–hole pairs in 2D-TMD monolayers opens a new horizon for the application of these materials. For instance, long-lived electron–hole pairs are appropriate for photovoltaic devices, but short-lived excitons are more beneficial for lasers with ultrashort pulses. 

This work explores the 2D interfacial energy transport between monolayer WSe₂and SiO₂while considering the thermal nonequilibrium between optical and acoustic phonons caused by photoexcitation. Recent modeling and experimental work have shown substantial temperature differences between optical and acoustic phonons (ΔT_OA) in various nanostructures upon laser irradiation. Generally, characterizations of interfacial thermal resistance (R′′_tc) at the nanoscale are difficult and depend on Raman‐probed temperature measurements, which only reveal optical phonon temperature information. Here it is shown that ΔT_OAfor supported monolayer WSe₂can be as high as 48% of the total temperature rise revealed by optothermal Raman methods—a significant proportion that can introduce sizeable error toR′′_tcmeasurements if not properly considered. A frequency energy transport state‐resolved Raman technique (FET‐Raman) along with a 3D finite volume modeling of 2D material laser heating is used to extract the true interfacial thermal resistanceR′′_tc(determined by acoustic phonon transport). Additionally, a novel ET‐Raman technique is developed to determine the energy coupling factorGbetween optical and acoustic phonons (on the order of 10¹⁵W m⁻³K⁻¹). This work demonstrates the need for special consideration of thermal nonequilibriums during laser–matter interactions at the nanoscale.