Symmetry Engineering in Twisted Bilayer WTe2.

The fabrication of artificial structures using a twisted van der Waals assembly has been a key technique for recent advancements in the research of two-dimensional (2D) materials. To date, various exotic phenomena have been observed thanks to the modified electron correlation or moiré structure controlled by the twist angle. However, the twisted van der Waals assembly has further potential to modulate the physical properties by controlling the symmetry. In this study, we fabricated twisted bilayer WTe2 and demonstrated that the twist angle successfully controls the spatial inversion symmetry and hence the spin splitting in the band structure. Our results reveal the further potential of a twisted van der Waals assembly, suggesting the feasibility of pursuing new physical phenomena in 2D materials based on the control of symmetry.

Dynamics of Moiré Trion and Its Valley Polarization in a Microfabricated WSe2/MoSe2 Heterobilayer.

The moiré potential, induced by stacking two monolayer semiconductors with slightly different lattice mismatches, acts as periodic quantum confinement for optically generated excitons, resulting in spatially ordered zero-dimensional quantum systems. However, there are limitations to exploring intrinsic optical properties of moiré excitons due to ensemble emissions and broadened emissions from many peaks caused by the inhomogeneity of the moiré potential. In this study, we proposed a microfabrication technique based on focused Ga+ ion beams, which enables us to control the number of peaks originating from the moiré potential and thus explore unknown moiré optical characteristics of WSe2/MoSe2 heterobilayer. By taking advantage of this approach, we reveal emissions from a single moiré exciton and charged moiré exciton (trion) under electrostatic doping conditions. We show the momentum dark moiré trion state above the bright trion state with a splitting energy of approximately 4 meV and clarify that the dynamics are determined by the initial trion population in the bright state. Furthermore, the degree of negative circularly polarized emissions and their valley dynamics of moiré trions are dominated by a very long valley relaxation process lasting ∼700 ns. Our findings on microfabricated heterobilayer could be viewed as an extension of our groundbreaking efforts in the field of quantum optics application using moiré superlattices.

Shift-Current Photovoltaics Based on a Non-Centrosymmetric Phase in In-Plane Ferroelectric SnS.

The shift-current photovoltaics of group-IV monochalcogenides has been predicted to be comparable to those of state-of-the-art Si-based solar cells. However, its exploration has been prevented from the centrosymmetric layer stacking in the thermodynamically stable bulk crystal. Herein, the non-centrosymmetric layer stacking of tin sulfide (SnS) is stabilized in the bottom regions of SnS crystals grown on a van der Waals substrate by physical vapor deposition and the shift current of SnS, by combining the polarization angle dependence and circular photogalvanic effect, is demonstrated. Furthermore, 180° ferroelectric domains in SnS are verified through both piezoresponse force microscopy and shift-current mapping techniques. Based on these results, an atomic model of the ferroelectric domain boundary is proposed. The direct observation of shift current and ferroelectric domains reported herein paves a new path for future studies on shift-current photovoltaics.

Continuous Color-Tunable Light-Emitting Devices Based on Compositionally Graded Monolayer Transition Metal Dichalcogenide Alloys.

The diverse series of transition metal dichalcogenide (TMDC) materials has been employed in various optoelectronic applications, such as photodetectors, light-emitting diodes, and lasers. Typically, the detection or emission range of optoelectronic devices is unique to the bandgap of the active material. Therefore, to improve the capability of these devices, extensive efforts have been devoted to tune the bandgap, such as gating, strain, and dielectric engineering. However, the controllability of these methods is severely limited (typically ≈0.1 eV). In contrast, alloying TMDCs is an effective approach that yields a composition-dependent bandgap and enables light emissions over a wide range. In this study, a color-tunable light-emitting device using compositionally graded TMDC alloys is fabricated. The monolayer WS2 /WSe2 alloy grown by chemical vapor deposition shows a spatial gradient in the light-emission energy, which varies from 2.1 to 1.7 eV. This alloy is incorporated in an electrolyte-based light-emitting device structure that can tune the recombination zone laterally. Thus, a continuous and reversible color-tunable light-emitting device is successfully fabricated by controlling the light-emitting positions. The results provide a new approach for exploring monolayer semiconductor-based broadband optical applications.

Valley Relaxation of the Moiré Excitons in a WSe2/MoSe2 Heterobilayer.

The moiré superlattice consisting of lattice- or angular-mismatched van der Waals heterostructures drastically changes the physical properties of constituent atomically thin materials by confinement of the exciton by the moiré potential, which is promising for next-generation quantum optics. The moiré superlattice also affects the valley degrees of freedom of the monolayer transition-metal dichalcogenides (TMDs) and the valley-dependent optical selection rule, which results in the characteristic circular polarized light emission of the moiré exciton. However, the valley relaxation process of excitons in the moiré superlattice remains to be understood. Here, we studied valley relaxation of moiré excitons in a twisted WSe2/MoSe2 heterobilayer by circularly polarized photoluminescence and photoluminescence excitation (PLE) spectroscopy. The experimentally observed circularly polarized emission strongly depends on the excitation power density, which contrasts with the case of two-dimensional monolayer TMDs. The excitation power-dependent circularly polarized emission suggests the characteristic valley relaxation of the moiré exciton with a small density of states in zero-dimensional systems. In addition, the resonant PLE measurement reveals the intravalley relaxation process from the triplet to singlet state of the moiré exciton via Γ5 phonon emission. Our findings clarified the valley relaxation of the moiré excitons, which would lead to the application of the circularly polarized quantum light emitter in twisted semiconducting heterobilayers.

Magnon-Coupled Intralayer Moiré Trion in Monolayer Semiconductor-Antiferromagnet Heterostructures.

Moiré fringe patterns created by stacking different 2D layered materials as artificial van der Waals (vdW) heterostructures have become a novel platform to study and engineer optically generated excitonic properties. The moiré patterns contribute to the formation of spatially ordered excitonic states (excitons and trions), which can be used in the quantum simulation of many-body systems and ensembles of coherent quantum light emitters. The intriguing moiré excitonic properties are affected by and controlled via the interaction with magnetic elements. Here, a moiré excitonic system interacting with the magnetic elementary excitation of antiferromagnetic orders in MoSe2 /MnPS3 vdW heterostructures is reported. The low-temperature photoluminescence spectra with additional fine spectral structures on the low-energy side, which are coupled magnon-trion peaks below the Néel temperature of MnPS3 , are carefully investigated. The fine spectral structures with long lifetime and coherence time are assigned to intralayer trion-magnon complexes trapped in the moiré potentials (moiré trion-magnon complexes). These findings highlight the emergence of moiré trion-magnon complexes and provide a new way to explore novel quantum phenomena in moiré excitonic systems with magnetic functionalities.

Resonant Coupling of a Moiré Exciton to a Phonon in a WSe2/MoSe2 Heterobilayer.

Moiré patterns with an angular mismatch in van der Waals heterostructures are a fascinating platform to engineer optically generated excitonic properties. The moiré pattern can give rise to spatially ordered exciton ensembles, which offer the possibility for coherent quantum emitters and quantum simulation of many-body physics. The intriguing moiré exciton properties are affected by their dynamics and exciton-phonon interaction. Here, we report the moiré exciton and phonon interaction in a twisted WSe2/MoSe2 heterobilayer. By tuning the excitation energy, we realized the selective excitation of the moiré exciton at phonon resonances and the otherwise negligible small absorption. Furthermore, we revealed the relaxation of moiré exciton ensembles between different potential minima via the resonant phonon scattering process. Our findings highlight resonant coupling of a moiré exciton to a phonon and could pave a new way for the exploration of novel quantum phenomena of the moiré exciton.

Ultralarge Photoluminescence Enhancement of Monolayer Molybdenum Disulfide by Spontaneous Superacid Nanolayer Formation.

Due to the direct band gap nature, extensive studies have been conducted to improve the optical behavior in monolayer transition metal dichalcogenides (TMDCs) with a formula of MX2 (M = Mo, W; X = S, Se, Te). One of the strongest modulating agents of optical behavior is a molecular superacid treatment; however, the chemical event has not been unveiled. Also, the engineering protocol for keeping the treatment is immature. In this work, we systematically study the superacid treatment procedures on monolayer molybdenum disulfide (MoS2) and propose that the interaction, a hydrophilic interaction, between the superacid molecule and MoS2 surface would be critical. As a result of the interaction, the superacid molecules spontaneously form an acidic layer with the thickness of several nanometers on the surface. The power-dependent photoluminescence (PL) measurement indicates the edge of MoS2 flake is more effective and electronically modulated by the treatment. By understanding the superacid nanolayer formation by the treatment, we succeeded in maintaining the ultrastrong PL in the superacid-treated MoS2 for more than 30 days in the ambient air by encapsulation with transparent organic polymers. This study advances the understanding and designing applications of strong luminescent properties in the superacid-treated TMDCs and paves the way toward engineering exciton dynamics and an experimental platform for treating multibody states.

Controllable Magnetic Proximity Effect and Charge Transfer in 2D Semiconductor and Double-Layered Perovskite Manganese Oxide van der Waals Heterostructure.

Optically generated excitonic states (excitons and trions) in transition metal dichalcogenides are highly sensitive to the electronic and magnetic properties of the materials underneath. Modulation and control of the excitonic states in a novel van der Waals (vdW) heterostructure of monolayer MoSe2 on double-layered perovskite Mn oxide ((La0.8 Nd0.2 )1.2 Sr1.8 Mn2 O7 ) is demonstrated, wherein the Mn oxide transforms from a paramagnetic insulator to a ferromagnetic metal. A discontinuous change in the exciton photoluminescence intensity via dielectric screening is observed. Further, a relatively high trion intensity is discovered due to the charge transfer from metallic Mn oxide under the Curie temperature. Moreover, the vdW heterostructures with an ultrathin h-BN spacer layer demonstrate enhanced valley splitting and polarization of excitonic states due to the proximity effect of the ferromagnetic spins of Mn oxide. The controllable h-BN thickness in vdW heterostructures reveals a several-nanometer-long scale of charge transfer as well as a magnetic proximity effect. The vdW heterostructure allows modulation and control of the excitonic states via dielectric screening, charge carriers, and magnetic spins.

Photoactivation of Strong Photoluminescence in Superacid-Treated Monolayer Molybdenum Disulfide.

To advance the development of atomically thin optoelectronics using two-dimensional (2D) materials, engineering strong luminescence with a physicochemical basis is crucial. Semiconducting monolayer transition-metal dichalcogenides (TMDCs) are candidates for this, but their quantum yield (QY) is known to be poor. Recently, a molecular superacid treatment of bis(trifluoromethane)sulfonimide (TFSI) generated unambiguously bright monolayer TMDCs and a high QY. However, this method is highly dependent on the processing conditions and therefore has not been generalized. Here, we shed light on environmental factors to activate the photoluminescence (PL) intensity of the TFSI-treated monolayer MoS2, with a factor of more than 2 orders of magnitude greater than the original by photoactivation. The method is useful for both mechanically exfoliated and chemically deposited samples. The existence of photoirradiation larger than the band gap demonstrates enhancement of the PL of MoS2; on the other hand, activation by thermal annealing, as demonstrated in the previous report, is less effective for enhancing the PL intensity. The photoactivated monolayer MoS2 shows a long lifetime of ∼1.35 ns, more than a 30-fold improvement over the original as exfoliated. The consistent realization of the bright monolayer MoS2 reveals that air exposure is an essential factor in the process. TFSI treatment in a N2 environment was not effective for achieving a strong PL, even after the photoactivation. These findings can serve as a basis for engineering the bright atomically thin materials for 2D optoelectronics.

Vapor Phase Selective Growth of Two-Dimensional Perovskite/WS2 Heterostructures for Optoelectronic Applications.

Organic-inorganic hybrid perovskites have attracted increased interest owing to their exceptional optoelectronic properties and promising applications. Monolayers of transition metal dichalcogenides (TMDCs), such as tungsten disulfide (WS2), are also intriguing because of their unique optoelectronic properties and their atomically thin and flexible structures. Therefore, the combination of these different types of materials is very attractive in terms of fundamental science of interface interaction, as well as for the realization of ultrathin optoelectronic devices with high performance. Here, we demonstrate the controlled synthesis of two-dimensional (2D) perovskite/WS2 heterostructures by an all vapor-phase growth approach. This involves the chemical vapor deposition (CVD) growth of monolayer WS2, followed by the vapor-phase selective deposition of 2D PbI2 onto the WS2 with the successive conversion of PbI2 to organic-inorganic perovskite (CH3NH3PbI3). Moreover, the selective growth of the perovskite on prepatterned WS2 enables the direct synthesis of patterned heterostructures, avoiding any damage to the perovskite. The photodetectors utilizing the perovskite/WS2 heterostructure show increased responsivities compared with isolated thin perovskite obtained by conventional solution methods. The integration of 2D perovskite with TMDCs opens a new avenue to fabricate advanced devices by combining their unique properties and overcoming current processing difficulties of perovskites.

Planar Perovskite Solar Cells with High Efficiency and Fill Factor Obtained Using Two-Step Growth Process.

Hybrid organic-inorganic perovskite solar cells (PSCs) have been regarded as the most promising next-generation photovoltaics (PVs) because of their potential for low-cost fabrication and advances in their development. Superior quality of the photoactive perovskite layer is a main factor for further increasing the PV performance of the organic-inorganic perovskite solar cells (PSCs). Herein, we successfully obtained perovskite with a high crystallinity and large grain size by utilizing excess PbI2 and SSGP technique and demonstrated a superior PV performance of normal-architecture planar PSCs. The SSGP PSCs with the highest fill factor (FF) reported thus far (83.4%) to our knowledge were obtained without sacrificing other PV parameters. Moreover, a high efficiency of 21.3% (21.6%) with a high FF of 80.0% (81.2%) in forward (reverse) scan was achieved. The unencapsulated SSGP PSCs showed robust continuous light-soaking and thermal stability under harsh characterization conditions. Additionally, we achieved a high efficiency of 20.1% with a negligible hysteresis on the large active area SSGP PSCs (∼1 cm2). The optical properties, efficient carrier extraction, and reduction of recombination loss of the SSGP perovskite significantly contribute to the high PV performance and robust stability of SSGP PSCs.

Carrier Transport and Photoresponse in GeSe/MoS2 Heterojunction p-n Diodes.

Simple stacking of thin van der Waals 2D materials with different physical properties enables one to create heterojunctions (HJs) with novel functionalities and new potential applications. Here, a 2D material p-n HJ of GeSe/MoS2 is fabricated and its vertical and horizontal carrier transport and photoresponse properties are studied. Substantial rectification with a very high contrast (>104 ) through the potential barrier in the vertical-direction tunneling of HJs is observed. The negative differential transconductance with high peak-to-valley ratio (>105 ) due to the series resistance change of GeSe, MoS2 , and HJs at different gate voltages is observed. Moreover, strong and broad-band photoresponse via the photoconductive effect are also demonstrated. The explored multifunctional properties of the GeSe/MoS2 HJs are expected to be important for understanding the carrier transport and photoresponse of 2D-material HJs for achieving their use in various new applications in the electronics and optoelectronics fields.

Hydrogen bond and lifetime dynamics in diluted alcohols.

Hydrogen-bonding plays a crucial role in many chemical and biochemical reactions. Alcohols, with their hydrophilic and hydrophobic groups, constitute an important class of hydrogen-bonding molecules with functional tuning possibilities through changes in the hydrophobic tails. Recent studies demonstrated that for solutions of alcohols changes in the hydrophobic tail significantly affect a broad range of dynamics properties of the liquid. Still, the understanding is lacking on the origin of such differences in terms of a solvent- versus a solute-dominated effect. Here we reveal this origin by studying hydrogen-bond dynamics in a number of alcohol molecules - from methanol to butanol - diluted in a hydrogen-bond accepting environment, acetonitrile. The dynamics were investigated by pump-probe and 2D infrared spectroscopy combined with molecular dynamics-spectral simulations, using the OH stretching mode as a reporter. For all the considered alcohols, the vibrational lifetime of the OH stretching mode was found to be ∼3 ps. The hydrogen-bond dynamics exhibit similar behavior with a fast (∼200 fs) initial relaxation dominated by librational motion and a slow (∼4 ps) relaxation due to hydrogen-bond exchange dynamics. The similar dynamics over such a broad range of alcohols led us to conclude that the previously observed differences in dynamics in bulk alcohols originate from the dependence of the solvent properties on the hydrophobic tail, while the solute properties as found herein are essentially independent of the hydrophobic tail.

Strong Amplification of Coherent Acoustic Phonons by Intraminiband Currents in a Semiconductor Superlattice.

Sound amplification in an electrically biased superlattice (SL) is studied in optical experiments with 100 fs time resolution. Coherent SL phonons with frequencies of 40, 375, and 410 GHz give rise to oscillatory reflectivity changes. With currents from 0.5 to 1.3 A, the Fourier amplitude of the 410 GHz phonon increases by more than a factor of 2 over a 200 ps period. This amplification is due to stimulated Cerenkov phonon emission by electrons undergoing intraminiband transport. The gain coefficient of 8×10^{3} cm^{-1} is reproduced by theoretical calculations and holds potential for novel sub-THz phonon emitters.

Hydrogen bond dynamics in bulk alcohols.

Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics-quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid--alcohols--has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.