Motion of Two-Dimensional Excitons in Momentum Space Leads to Pseudospin Distribution Narrowing on the Bloch Sphere.

Motional narrowing implies narrowing induced by motion; for example, in nuclear magnetic resonance, the thermally induced random motion of the nuclei in an inhomogeneous environment leads to a counterintuitive narrowing of the resonance line. Similarly, the excitons in monolayer semiconductors experience magnetic inhomogeneity: the electron-hole spin-exchange interaction manifests as an in-plane pseudomagnetic field with a periodically varying orientation inside the exciton band. The excitons undergo random momentum scattering and pseudospin precession repeatedly in this inhomogeneous magnetic environment, typically resulting in fast exciton depolarization. On the contrary, we show that such magnetic inhomogeneity averages out at high scattering rates due to motional narrowing. Physically, a faster exciton scattering leads to a narrower pseudospin distribution on the Bloch sphere, implying a nontrivial improvement in exciton polarization. The in-plane nature of the pseudomagnetic field enforces a contrasting scattering dependence between the circularly and linearly polarized excitons, providing a spectroscopic way to gauge the sample quality.

Harmonic to anharmonic tuning of moiré potential leading to unconventional Stark effect and giant dipolar repulsion in WS2/WSe2 heterobilayer.

Excitonic states trapped in harmonic moiré wells of twisted heterobilayers is an intriguing testbed for exploring many-body physics. However, the moiré potential is primarily governed by the twist angle, and its dynamic tuning remains a challenge. Here we demonstrate anharmonic tuning of moiré potential in a WS2/WSe2 heterobilayer through gate voltage and optical power. A gate voltage can result in a local in-plane perturbing field with odd parity around the high-symmetry points. This allows us to simultaneously observe the first (linear) and second (parabolic) order Stark shift for the ground state and first excited state, respectively, of the moiré trapped exciton - an effect opposite to conventional quantum-confined Stark shift. Depending on the degree of confinement, these excitons exhibit up to twenty-fold gate-tunability in the lifetime (100 to 5 ns). Also, exciton localization dependent dipolar repulsion leads to an optical power-induced blueshift of ~ 1 meV/µW - a five-fold enhancement over previous reports.

Observation of ~100% valley-coherent excitons in monolayer MoS2 through giant enhancement of valley coherence time.

In monolayer transition metal dichalcogenide semiconductors, valley coherence degrades rapidly due to a combination of fast scattering and inter-valley exchange interaction. This leads to a sub-picosecond valley coherence time, making coherent manipulation of exciton a highly challenging task. Using monolayer MoS2 sandwiched between top and bottom graphene, here we demonstrate fully valley-coherent excitons by observing ~100% degree of linear polarization in steady state photoluminescence. This is achieved in this unique design through a combined effect of (a) suppression in exchange interaction due to enhanced dielectric screening, (b) reduction in exciton lifetime due to a fast inter-layer transfer to graphene, and (c) operating in the motional narrowing regime. We disentangle the role of the key parameters affecting valley coherence by using a combination of calculation (solutions of Bethe-Salpeter and Maialle-Silva-Sham equations) and a careful choice of design of experiments using four different stacks with systematic variation of screening and exciton lifetime. To the best of our knowledge, this is the first report in which the excitons are found to be valley coherent in the entire lifetime in monolayer semiconductors, allowing optical readout of valley coherence possible.

Electrically Tunable Localized versus Delocalized Intralayer Moiré Excitons and Trions in a Twisted MoS2 Bilayer.

Moiré superlattice (mSL)-induced sub-bands in twisted van der Waals homo- and heterostructures govern their optical and electrical properties, rendering additional degrees of freedom such as twist angle. Here, we demonstrate the moiré superlattice effects on the intralayer excitons and trions in a twisted bilayer of MoS2 of H-type stacking at marginal twist angles. We identify the emissions from localized and delocalized sub-bands of intralayer moiré excitons and show their electrical modulation by the corresponding trion formation. The electrical control of the oscillator strength of the moiré excitons also results in the strong tunability of resonant Raman scattering. We find that the gate-induced doping significantly modulates the electronic moiré potential; however, leaves the excitonic moiré confinement unaltered. This effect, coupled with variable moiré trap filling by tuning the optical excitation density, allows us to delineate the different phases of localized and delocalized moiré trions. We demonstrate that the moiré excitons exhibit strong valley coherence that changes in a striking nonmonotonic W-shape with gating due to motional narrowing. These observations from the simultaneous electrostatic control of quasiparticle-dependent moiré potential will lead to exciting effects of tunable many-body phenomena in moiré superlattices.

Highly Nonlinear Biexcitonic Photocurrent from Ultrafast Interlayer Charge Transfer.

Strong Coulomb interactions in monolayer semiconductors allow them to host optically active large many-body states, such as the five-particle state, charged biexciton. Strong nonlinear light absorption by the charged biexciton under spectral resonance, coupled with its charged nature, makes it intriguing for nonlinear photodetection─an area that is hitherto unexplored. Using the high built-in vertical electric field in an asymmetrically designed few-layer graphene encapsulated 1L-WS2 heterostructure, here we report a large, highly nonlinear photocurrent arising from the strong absorption by two charged biexciton species under zero external bias (self-powered mode). Time-resolved measurement reveals that the generated charged biexcitons transfer to the few-layer graphene in a time scale of sub-5 ps, indicating an ultrafast intrinsic limit of the photoresponse. By using single- and two-color photoluminescence excitation spectroscopy, we show that the two biexcitonic peaks originate from bright-dark and bright-bright exciton-trion combinations. Such innate nonlinearity in the photocurrent due to its biexcitonic origin, coupled with the ultrafast response due to swift interlayer charge transfer, exemplifies the promise of manipulating many-body effects in monolayers toward viable optoelectronic applications.

A High-Quality Entropy Source Using van der Waals Heterojunction for True Random Number Generation.

Generators of random sequences used in high-end applications such as cryptography rely on entropy sources for their indeterminism. Physical processes governed by the laws of quantum mechanics are excellent sources of entropy available in nature. However, extracting enough entropy from such systems for generating truly random sequences is challenging while maintaining the feasibility of the extraction procedure for real-world applications. Here, we present a compact and an all-electronic van der Waals heterostructure-based device capable of detecting discrete charge fluctuations for extracting entropy from physical processes and use it for the generation of independent and identically distributed true random sequences. We extract a record-high value (>0.98 bits/bit) of min-entropy using the proposed scheme. We demonstrate an entropy generation rate tunable over multiple orders of magnitude and show the persistence of the underlying physical process for temperatures ranging from cryogenic to ambient conditions. We verify the random nature of the generated sequences using tests such as NIST SP 800-90B standard and other statistical measures and verify the suitability of our random sequence for cryptographic applications using the NIST SP 800-22 standard. The generated random sequences are then used in implementing various randomized algorithms without any preconditioning steps.

Negative Differential Photoconductance as a Signature of Nonradiative Energy Transfer in van der Waals Heterojunction.

The physical proximity of layered materials in their van der Waals heterostructures (vdWhs) aids interfacial phenomena such as charge transfer (CT) and energy transfer (ET). Besides providing fundamental insights, CT and ET also offer routes to engineer optoelectronic properties of vdWhs. For example, harnessing ET in vdWhs can help to overcome the limitations of optical absorption imposed by the ultra-thin nature of layered materials and thus provide an opportunity for in situ enhancement of quantum efficiency for light-harvesting and sensing applications. While several spectroscopic studies on vdWhs probed the dynamics of CT and ET, the possible contribution of ET in the photocurrent generation remains largely unexplored. In this work, we investigate the role of nonradiative energy transfer (NRET) in the photocurrent through a vertical vdWh of SnSe2/MoS2/TaSe2. We observe an unusual negative differential photoconductance (NDPC) arising from the existence of NRET across the SnSe2/MoS2 junction. Modulation of the NRET-driven NDPC characteristics with optical power results in a striking transition of the photocurrent's power law from a sublinear to a superlinear regime. Our observations reveal the nontrivial influence of ET on the photoresponse of vdWhs, which offer insights to harness ET in synergy with CT for vdWh based next-generation optoelectronics.

Strong near band-edge excited second-harmonic generation from multilayer 2H Tin diselenide.

We report strong second-harmonic generation (SHG) from 2H polytype of multilayer Tin diselenide (SnSe2) for fundamental excitation close to the indirect band-edge in the absence of excitonic resonances. Comparison of SHG and Raman spectra from exfoliated SnSe2 flakes of different polytypes shows strong (negligible) SHG and Raman Eg mode at 109 cm-1 (119 cm-1), consistent with 2H (1T) polytypes. The difference between the A1g-Eg Raman peak positions is found to exhibit significant thickness dependent for the 1T form, which is found to be absent for the 2H form. The observed thickness dependence of SHG with rapid oscillations in signal strength for small changes in flake thickness are in good agreement with a nonlinear wave propagation model considering nonlinear polarization with alternating sign from each monolayer. The nonlinear optical susceptibility extracted from SHG signal comparison with standard quartz samples for 1040 nm excitation is found to be more than 4-times higher than that at 1550 nm. This enhanced nonlinear response at 1040 nm is attributed to the enhanced nonlinear optical response for fundamental excitation close to the indirect band-edge. We also study SHG from heterostructures of monolayer MoS2/multilayer SnSe2 which allows us to unambiguously compare the nonlinear optical response of SnSe2 with MoS2. We find the SHG signal and any interference effect in the overlap region to be dominated by the SnSe2 layer for the excitation wavelengths considered. The comparison of SHG from SnSe2 and MoS2 underscores that the choice of the 2D material for a particular nonlinear optical application is contextual on the wavelength range of interest and its optical properties at those wavelengths. The present works further highlights the usefulness of near band-edge enhancement of nonlinear processes in emerging 2D materials towards realizing useful nanophotonic devices.

Polarization independent enhancement of zeroth order diffracted second harmonic from multilayer gallium selenide on a silicon resonant metasurface.

We demonstrate polarization-independent resonant-enhancement of second harmonic generation (SHG) from multilayer Gallium Selenide (GaSe) on a silicon-based resonant metasurface. Two-dimensional hexagonal photonic lattice with circularly symmetric silicon meta-atoms are designed to achieve resonant field enhancement at the fundamental wavelength independent of the incident polarization direction. Such structures are however found to exhibit strong resonant field depolarization effects at the fundamental excitation fields resulting in modified nonlinear polarization components when compared to the native GaSe layer. Furthermore, the sub-wavelength metasurface designed to have resonances at the fundamental wavelengths act as a higher order diffraction grating at the second harmonic wavelength. Nonlinear wave propagation simulations show that the higher order diffracted SHG exhibit strong polarization dependent enhancement with characteristics very different from the native GaSe layer. In this context, polarization independent enhancement of the second harmonic signal is achieved only for the zeroth order diffracted component. Experimental study of second harmonic generation from the GaSe layer integrated with the silicon metasurface shows maximum nonlinear signal enhancement on-resonance with polarization dependence identical to the native GaSe layer by selectively detecting the zeroth-order diffracted component. This work shows that it is not sufficient to use symmetric meta-atoms in such 2D material integrated resonant metasurfaces for achieving polarization independent nonlinear optical enhancement. Depolarization of the resonant fields and higher-order diffraction at the nonlinear signal wavelength need to be considered as well.

Astability versus Bistability in van der Waals Tunnel Diode for Voltage Controlled Oscillator and Memory Applications.

van der Waals (vdW) tunnel junctions are attractive because of their atomically sharp interface, gate tunability, and robustness against lattice mismatch between the successive layers. However, the negative differential resistance (NDR) demonstrated in this class of tunnel diodes often exhibits noisy behavior with low peak current density and lacks robustness and repeatability, limiting their practical circuit applications. Here, we propose a strategy of using a 1L-WS2 as an optimum tunnel barrier sandwiched in a broken gap tunnel junction of highly doped black phosphorus (BP) and SnSe2. We achieve high yield tunnel diodes exhibiting highly repeatable, ultraclean, and gate-tunable NDR characteristics with a signature of intrinsic oscillation, and a large peak-to-valley current ratio (PVCR) of 3.6 at 300 K (4.6 at 7 K), making them suitable for practical applications. We show that the thermodynamic stability of the vdW tunnel diode circuit can be tuned from astability to bistability by altering the constraint through choosing a voltage or a current bias, respectively. In the astable mode under voltage bias, we demonstrate a compact, voltage-controlled oscillator without the need for an external tank circuit. In the bistable mode under current bias, we demonstrate a highly scalable, single-element, one-bit memory cell that is promising for dense random access memory applications in memory intensive computation architectures.

Combinatorial Large-Area MoS2/Anatase-TiO2 Interface: A Pathway to Emergent Optical and Optoelectronic Functionalities.

The interface of transition-metal dichalcogenides (TMDCs) and high-k dielectric transition-metal oxides (TMOs) had triggered umpteen discourses because of the indubitable impact of TMOs in reducing the contact resistances and restraining the Fermi-level pinning for the metal-TMDC contacts. In the present work, we focus on the unresolved tumults of large-area TMDC/TMO interfaces, grown by adopting different techniques. Here, on a pulsed laser-deposited MoS2 thin film, a layer of TiO2 is grown by atomic layer deposition (ALD) and pulsed laser deposition (PLD). These two different techniques emanate the layer of TiO2 with different crystallinities, thicknesses, and interfacial morphologies, subsequently influencing the electronic and optical properties of the interfaces. Contrasting the earlier reports of n-type doping at the exfoliated MoS2/TiO2 interfaces, the large-area MoS2/anatase-TiO2 films had realized a p-type doping of the underneath MoS2, manifesting a boost in the extent of p-type doping with increasing thickness of TiO2, as emerged from the X-ray photoelectron spectra. Density functional analysis of the MoS2/anatase-TiO2 interfaces, with pristine and interfacial defect configurations, could correlate the interdependence of doping and the terminating atomic surface of TiO2 on MoS2. The optical properties of the interface, encompassing photoluminescence, transient absorption and z-scan two-photon absorption, indicate the presence of defect-induced localized midgap levels in MoS2/TiO2 (PLD) and a relatively defect-free interface in MoS2/TiO2 (ALD), corroborating nicely with the corresponding theoretical analysis. From the investigation of optical properties, we indicate that the MoS2/TiO2 (PLD) interface may act as a promising saturable absorber, having a significant nonlinear response for the sub-band-gap excitations. Moreover, the MoS2/TiO2 (PLD) interface had exemplified better phototransport properties. A potential application of MoS2/TiO2 (PLD) is demonstrated by the fabrication of a p-type phototransistor with the ionic-gel top gate. This endeavor to analyze and perceive the MoS2/TiO2 interface establishes the prospectives of large-area interfaces in the field of optics and optoelectronics.

Gate- and Light-Tunable Negative Differential Resistance with High Peak Current Density in 1T-TaS2/2H-MoS2 T-Junction.

Metal-based electronics is attractive for fast and radiation-hard electronic circuits and remains one of the long-standing goals for researchers. The emergence of 1T-TaS2, a layered material exhibiting strong charge density wave (CDW)-driven resistivity switching that can be controlled by an external stimulus such as electric field and optical pulses, has triggered a renewed interest in metal-based electronics. Here we demonstrate a negative differential resistor (NDR) using electrically driven CDW phase transition in an asymmetrically designed T-junction made up of 1T-TaS2/2H-MoS2 van der Waals heterojunction. The principle of operation of the proposed device is governed by majority carrier transport and is distinct from usual NDR devices employing tunneling of carriers; thus it avoids the bottleneck of weak tunneling efficiency in van der Waals heterojunctions. Consequently, we achieve a peak current density in excess of 105 nA µm-2, which is about 2 orders of magnitude higher than that obtained in typical layered material based NDR implementations. The peak current density can be effectively tuned by an external gate voltage as well as photogating. The device is robust against ambiance-induced degradation, and the characteristics repeat in multiple measurements over a period of more than a month. The findings are attractive for the implementation of active metal-based functional circuits.

Third-harmonic generation in multilayer Tin Diselenide under the influence of Fabry-Perot interference effects.

Two-dimensional layered materials are in general known to exhibit strong layer dependent nonlinear optical response owing to the crystal symmetry and associated phase matching considerations. Here we report up-conversion of 1550 nm incident light using third-harmonic generation (THG) in multilayered tin di-selenide (SnSe2) and study its thickness dependence by simultaneously acquiring spatially-resolved images in the forward and backward propagation direction. We find good agreement between the experimental measurements and a coupled-wave equation model we have developed when including the effect of Fabry-Perot interference between the SnSe2 layer and the surrounding medium. We extract the magnitude of the third order electronic nonlinear optical susceptibility of SnSe2, for the first time to our knowledge, by comparing its nonlinear response with a glass substrate and find this to be ∼1500 times higher than that of glass. We also study the polarization dependence and find good agreement with the expected angular dependence of nonlinear polarization considering the crystal symmetry of SnSe2. The large nonlinear optical susceptibility of multi-layer SnSe2 makes it a promising material for studying nonlinear optical effects. This work demonstrates that in addition to the large inherent nonlinear optical susceptibility, the high refractive index of these materials and optical absorption above the bandgap strongly influence the overall nonlinear optical response and its thickness dependence characteristics.

Highly Sensitive, Fast Graphene Photodetector with Responsivity >106 A/W Using a Floating Quantum Well Gate.

Graphene, owing to its zero-band-gap electronic structure, is promising as an absorption material for ultra-wideband photodetection applications. However, graphene-absorption-based detectors inherently suffer from poor responsivity because of weak absorption and fast photocarrier recombination, limiting their viability for low-intensity light detection. Here, we use a graphene/WS2/MoS2 vertical heterojunction to demonstrate a highly sensitive photodetector, where the graphene layer serves dual purposes, namely, as the light absorption layer and also as the carrier conduction channel, thus maintaining the broadband nature of the photodetector. A fraction of the photoelectrons in graphene encounter ultrafast interlayer transfer to a floating monolayer MoS2 quantum well, providing a strong quantum-confined photogating effect. The photodetector shows a responsivity of 4.4 × 106 A/W at 30 fW incident power, outperforming photodetectors reported till date where graphene is used as a light absorption material by several orders. In addition, the proposed photodetector exhibits an extremely low noise equivalent power of <4 fW/ Hz and a fast response (∼milliseconds) with zero reminiscent photocurrent. The findings are attractive toward the demonstration of a graphene-based highly sensitive, fast, broadband photodetection technology.

Strong Single- and Two-Photon Luminescence Enhancement by Nonradiative Energy Transfer across Layered Heterostructure.

The strong light-matter interaction in monolayer transition metal dichalcogenides (TMDs) is promising for nanoscale optoelectronics with their direct band gap nature and the ultrafast radiative decay of the strongly bound excitons these materials host. However, the impeded amount of light absorption imposed by the ultrathin nature of the monolayers impairs their viability in photonic applications. Using a layered heterostructure of a monolayer TMD stacked on top of strongly absorbing, nonluminescent, multilayer SnSe2, we show that both single-photon and two-photon luminescence from the TMD monolayer can be enhanced by a factor of 14 and 7.5, respectively. This is enabled through interlayer dipole-dipole coupling induced nonradiative Förster resonance energy transfer (FRET) from SnSe2 underneath, which acts as a scavenger of the light unabsorbed by the monolayer TMD. The design strategy exploits the near-resonance between the direct energy gap of SnSe2 and the excitonic gap of monolayer TMD, the smallest possible separation between donor and acceptor facilitated by van der Waals heterojunction, and the in-plane orientation of dipoles in these layered materials. The FRET-driven uniform single- and two-photon luminescence enhancement over the entire junction area is advantageous over the local enhancement in quantum dot or plasmonic structure integrated 2D layers and is promising for improving quantum efficiency in imaging, optoelectronic, and photonic applications.

Gate-Tunable WSe2/SnSe2 Backward Diode with Ultrahigh-Reverse Rectification Ratio.

Backward diodes conduct more efficiently in the reverse bias than in the forward bias, providing superior high-frequency response, temperature stability, radiation hardness, and 1/f noise performance than a conventional diode conducting in the forward direction. Here, we demonstrate a van der Waals material-based backward diode by exploiting the giant staggered band offsets of WSe2/SnSe2 vertical heterojunction. The diode exhibits an ultrahigh-reverse rectification ratio (R) of ∼2.1 × 104, and the same is maintained up to an unusually large bias of 1.5 V-outperforming existing backward diode reports using conventional bulk semiconductors as well as one- and two-dimensional materials by more than an order of magnitude while maintaining an impressive curvature coefficient (γ) of ∼37 V-1. The transport mechanism in the diode is shown to be efficiently tunable by external gate and drain bias, as well as by the thickness of the WSe2 layer and the type of metal contacts used. These results pave the way for practical electronic circuit applications using two-dimensional materials and their heterojunctions.

Asymmetrically Encapsulated Vertical ITO/MoS2 /Cu2 O Photodetector with Ultrahigh Sensitivity.

Strong light absorption, coupled with moderate carrier transport properties, makes 2D layered transition metal dichalcogenide semiconductors promising candidates for low intensity photodetection applications. However, the performance of these devices is severely bottlenecked by slow response with persistent photocurrent due to long lived charge trapping, and nonreliable characteristics due to undesirable ambience and substrate effects. Here ultrahigh specific detectivity (D*) of 3.2 × 1014 Jones and responsivity (R) of 5.77 × 104 A W-1 are demonstrated at an optical power density (Pop ) of 0.26 W m-2 and external bias (Vext ) of -0.5 V in an indium tin oxide/MoS2 /copper oxide/Au vertical multi-heterojunction photodetector exhibiting small carrier transit time. The active MoS2 layer being encapsulated by carrier collection layers allows us to achieve repeatable characteristics over large number of cycles with negligible trap assisted persistent photocurrent. A large D* > 1014 Jones at zero external bias is also achieved due to the built-in field of the asymmetric photodetector. Benchmarking the performance against existing reports in literature shows a viable pathway for achieving reliable and highly sensitive photodetectors for ultralow intensity photodetection applications.

Substrate effects in high gain, low operating voltage SnSe2 photoconductor.

High gain photoconductive devices find wide spread applications in low intensity light detection. Ultra-thin layered materials have recently drawn a lot of attention from researchers in this regard. However, in general, a large operating voltage is required to obtain large responsivity in these devices. In addition, the characteristics are often confounded by substrate induced trap effects. Here we report multi-layer SnSe2 based photoconductive devices using two different structures: (1) SiO2 substrate supported inter-digitated electrode (IDE), and (2) suspended channel. The IDE device exhibits a responsivity of [Formula: see text] A W-1 and [Formula: see text] A W-1 at operating voltages of 1 mV and 100 mV, respectively-a superior low voltage performance over existing literature on planar 2D structures. However, the responsivity reduces by more than two orders of magnitude, while the transient response improves for the suspended device-providing insights into the critical role played by the channel-substrate interface in the gain mechanism. The results, on one hand, are promising for highly sensitive photoconductive applications consuming ultra-low power, and on the other hand, show a generic methodology that could be applied to other layered material based photoconductive devices as well for extracting the intrinsic behavior.

Photoresponse of atomically thin MoS2 layers and their planar heterojunctions.

MoS2 monolayers exhibit excellent light absorption and large thermoelectric power, which are, however, accompanied by a very strong exciton binding energy - resulting in complex photoresponse characteristics. We study the electrical response to scanning photo-excitation on MoS2 monolayer (1L) and bilayer (2L) devices, and also on monolayer/bilayer (1L/2L) planar heterojunction and monolayer/few-layer/multi-layer (1L/FL/ML) planar double heterojunction devices to unveil the intrinsic mechanisms responsible for photocurrent generation in these materials and junctions. A strong photoresponse modulation is obtained by scanning the position of the laser spot, as a consequence of controlling the relative dominance of a number of layer dependent properties, including (i) the photoelectric effect (PE), (ii) the photothermoelectric effect (PTE), (iii) the excitonic effect, (iv) hot photo-electron injection from metal, and (v) carrier recombination. The monolayer and bilayer devices show a peak photoresponse when the laser is focused at the source junction, while the peak position shifts to the monolayer/few-layer junction in the heterostructure devices. The photoresponse is found to be dependent on the incoming light polarization when the source junction is illuminated, although the polarization sensitivity drastically reduces at the monolayer/few-layer heterojunction. Finally, we investigate the laser position dependent transient response of the photocurrent to reveal that trapping of carriers in SiO2 at the source junction is a critical factor to determine the transient response in 2D photodetectors, and also show that, by a systematic device design, such trapping can be avoided in the heterojunction devices, resulting in a fast transient response. The insights obtained will play an important role in designing a fast 2D TMD based photodetector and related optoelectronic and thermoelectric devices.

Valley-Coherent Hot Carriers and Thermal Relaxation in Monolayer Transition Metal Dichalcogenides.

We show room-temperature valley coherence in MoS2, MoSe2, WS2, and WSe2 monolayers using linear polarization-resolved hot photoluminescence (PL) at energies close to the excitation, demonstrating preservation of valley coherence before sufficient scattering events. The features of the copolarized hot luminescence allow us to extract the lower bound of the binding energy of the A exciton in monolayer MoS2 as 0.42 (±0.02) eV. The broadening of the PL peak is found to be dominated by a Boltzmann-type hot luminescence tail, and using the slope of the exponential decay, the carrier temperature is extracted in situ at different stages of energy relaxation. The temperature of the emitted optical phonons during the relaxation process is probed by exploiting the corresponding broadening of the Raman peaks due to temperature-induced anharmonic effects. The findings provide a physical picture of photogeneration of valley-coherent hot carriers and their subsequent energy relaxation pathways.