Correlation-driven nonequilibrium exciton site transition in a WSe2/WS2 moiré supercell.

Moiré superlattices of transition metal dichalcogenides offer a unique platform to explore correlated exciton physics with optical spectroscopy. Whereas the spatially modulated potentials evoke that the exciton resonances are distinct depending on a site in a moiré supercell, there have been no clear demonstration how the moiré excitons trapped in different sites dynamically interact with the doped carriers; so far the exciton-electron dynamic interactions were presumed to be site-dependent. Thus, the transient emergence of nonequilibrium correlations are open questions, but existing studies are limited to steady-state optical measurements. Here we report experimental fingerprints of site-dependent exciton correlations under continuous-wave as well as ultrashort optical excitations. In near-zero angle-aligned WSe2/WS2 heterobilayers, we observe intriguing polarization switching and strongly enhanced Pauli blocking near the Mott insulating state, dictating the dominant correlation-driven effects. When the twist angle is near 60°, no such correlations are observed, suggesting the strong dependence of atomic registry in moiré supercell configuration. Our studies open the door to largely unexplored nonequilibrium correlations of excitons in moiré superlattices.

Spinful hinge states in the higher-order topological insulators WTe2.

Higher-order topological insulators are recently discovered quantum materials exhibiting distinct topological phases with the generalized bulk-boundary correspondence. Td-WTe2 is a promising candidate to reveal topological hinge excitation in an atomically thin regime. However, with initial theories and experiments focusing on localized one-dimensional conductance only, no experimental reports exist on how the spin orientations are distributed over the helical hinges-this is critical, yet one missing puzzle. Here, we employ the magneto-optic Kerr effect to visualize the spinful characteristics of the hinge states in a few-layer Td-WTe2. By examining the spin polarization of electrons injected from WTe2 to graphene under external electric and magnetic fields, we conclude that WTe2 hosts a spinful and helical topological hinge state protected by the time-reversal symmetry. Our experiment provides a fertile diagnosis to investigate the topologically protected gapless hinge states, and may call for new theoretical studies to extend the previous spinless model.

Two-dimensional Dirac plasmon-polaritons in graphene, 3D topological insulator and hybrid systems.

Collective oscillations of massless particles in two-dimensional (2D) Dirac materials offer an innovative route toward implementing atomically thin devices based on low-energy quasiparticle interactions. Strong confinement of near-field distribution on the 2D surface is essential to demonstrate extraordinary optoelectronic functions, providing means to shape the spectral response at the mid-infrared (IR) wavelength. Although the dynamic polarization from the linear response theory has successfully accounted for a range of experimental observations, a unified perspective was still elusive, connecting the state-of-the-art developments based on the 2D Dirac plasmon-polaritons. Here, we review recent works on graphene and three-dimensional (3D) topological insulator (TI) plasmon-polariton, where the mid-IR and terahertz (THz) radiation experiences prominent confinement into a deep-subwavelength scale in a novel optoelectronic structure. After presenting general light-matter interactions between 2D Dirac plasmon and subwavelength quasiparticle excitations, we introduce various experimental techniques to couple the plasmon-polaritons with electromagnetic radiations. Electrical and optical controls over the plasmonic excitations reveal the hybridized plasmon modes in graphene and 3D TI, demonstrating an intense near-field interaction of 2D Dirac plasmon within the highly-compressed volume. These findings can further be applied to invent optoelectronic bio-molecular sensors, atomically thin photodetectors, and laser-driven light sources.

An Efficacious Transgenic Strategy for Triple Knockout of Xeno-Reactive Antigen Genes GGTA1, CMAH, and B4GALNT2 from Jeju Native Pigs.

Pigs are promising donors of biological materials for xenotransplantation; however, cell surface carbohydrate antigens, including galactose-alpha-1,3-galactose (α-Gal), N-glycolylneuraminic acid (Neu5Gc), and Sd blood group antigens, play a significant role in porcine xenograft rejection. Inactivating swine endogenous genes, including GGTA1, CMAH, and B4GALNT2, decreases the binding ratio of human IgG/IgM in peripheral blood mononuclear cells and erythrocytes and impedes the effectiveness of α-Gal, Neu5Gc, and Sd, thereby successfully preventing hyperacute rejection. Therefore, in this study, an effective transgenic system was developed to target GGTA1, CMAH, and B4GALNT2 using CRISPR-CAS9 and develop triple-knockout pigs. The findings revealed that all three antigens (α-Gal, Neu5Gc, and Sd) were not expressed in the heart, lungs, or liver of the triple-knockout Jeju Native Pigs (JNPs), and poor expression of α-Gal and Neu5G was confirmed in the kidneys. Compared with the kidney, heart, and lung tissues from wild-type JNPs, those from GGTA1/CMAH/ B4GALNT2 knockout-recipient JNPs exhibited reduced human IgM and IgG binding and expression of each immunological rejection component. Hence, reducing the expression of swine xenogeneic antigens identifiable by human immunoglobulins can lessen the immunological rejection against xenotransplantation. The findings support the possibility of employing knockout JNP organs for xenogeneic transplantation to minimize or completely eradicate rejection using multiple gene-editing methods.

Heteroepitaxial van der Waals semiconductor superlattices.

A broad range of transition metal dichalcogenide (TMDC) semiconductors are available as monolayer (ML) crystals, so the precise integration of each kind into van der Waals (vdW) superlattices (SLs) could enable the realization of novel structures with previously unexplored functionalities. Here we report the atomic layer-by-layer epitaxial growth of vdW SLs with programmable stacking periodicities, composed of more than two kinds of dissimilar TMDC MLs, such as MoS2, WS2 and WSe2. Using kinetics-controlled vdW epitaxy in the near-equilibrium limit by metal-organic chemical vapour depositions, we achieved precise ML-by-ML stacking, free of interlayer atomic mixing, which resulted in tunable two-dimensional vdW electronic systems. As an example, by exploiting the series of type II band alignments at coherent two-dimensional vdW heterointerfaces, we demonstrated valley-polarized carrier excitations-one of the most distinctive electronic features in vdW ML semiconductors-which scale with the stack numbers n in our (MoS2/WS2)n SLs on optical excitations.

Ultrafast non-excitonic valley Hall effect in MoS2/WTe2 heterobilayers.

The valley Hall effect (VHE) in two-dimensional (2D) van der Waals (vdW) crystals is a promising approach to study the valley pseudospin. Most experiments so far have used bound electron-hole pairs (excitons) through local photoexcitation. However, the valley depolarization of such excitons is fast, so that several challenges remain to be resolved. We address this issue by exploiting a unipolar VHE using a heterobilayer made of monolayer MoS2/WTe2 to exhibit a long valley-polarized lifetime due to the absence of electron-hole exchange interaction. The unipolar VHE is manifested by reduced photoluminescence at the MoS2 A exciton energy. Furthermore, we provide quantitative information on the time-dependent valley Hall dynamics by performing the spatially-resolved ultrafast Kerr-rotation microscopy; we find that the valley-polarized electrons persist for more than 4 nanoseconds and the valley Hall mobility exceeds 4.49 × 103 cm2/Vs, which is orders of magnitude larger than previous reports.

Polarization Selective Color Filter Based on Plasmonic Nanograting Embedded Etalon Structures.

In this paper, we propose a polarization-selective color filter that can generate two different color informations simultaneously depending on the polarization direction. The proposed color filter is mainly composed of the etalon structure to generate the color by the structural resonance properties while the upper layer of the etalon is made of plasmonic nanogratings to promote polarization-dependent color properties. When the duty ratio of the silver nanogratings is fixed, the proposed color filter can maintain identical optical properties for orthogonal polarization, while the etalon structure of the proposed color filter can manipulate different color information depending on the cavity height for the horizontal polarization. Finally, we experimentally confirm that polarization-dependent security images can be generated using the proposed color filters with a fixed duty ratio of various nanograting arrays.

Near-field sub-diffraction photolithography with an elastomeric photomask.

Photolithography is the prevalent microfabrication technology. It needs to meet resolution and yield demands at a cost that makes it economically viable. However, conventional far-field photolithography has reached the diffraction limit, which imposes complex optics and short-wavelength beam source to achieve high resolution at the expense of cost efficiency. Here, we present a cost-effective near-field optical printing approach that uses metal patterns embedded in a flexible elastomer photomask with mechanical robustness. This technique generates sub-diffraction patterns that are smaller than 1/10th of the wavelength of the incoming light. It can be integrated into existing hardware and standard mercury lamp, and used for a variety of surfaces, such as curved, rough and defect surfaces. This method offers a higher resolution than common light-based printing systems, while enabling parallel-writing. We anticipate that it will be widely used in academic and industrial productions.

Carrier multiplication in van der Waals layered transition metal dichalcogenides.

Carrier multiplication (CM) is a process in which high-energy free carriers relax by generation of additional electron-hole pairs rather than by heat dissipation. CM is promising disruptive improvements in photovoltaic energy conversion and light detection technologies. Current state-of-the-art nanomaterials including quantum dots and carbon nanotubes have demonstrated CM, but are not satisfactory owing to high-energy-loss and inherent difficulties with carrier extraction. Here, we report CM in van der Waals (vdW) MoTe2 and WSe2 films, and find characteristics, commencing close to the energy conservation limit and reaching up to 99% CM conversion efficiency with the standard model. This is demonstrated by ultrafast optical spectroscopy with independent approaches, photo-induced absorption, photo-induced bleach, and carrier population dynamics. Combined with a high lateral conductivity and an optimal bandgap below 1 eV, these superior CM characteristics identify vdW materials as an attractive candidate material for highly efficient and mechanically flexible solar cells in the future.

Light Polarization-Controlled Conversion of Ultrafast Coherent-Incoherent Exciton Dynamics in Few-Layer ReS2.

Coherent light-matter interaction can transiently modulate the quantum states of matter under nonresonant laser excitation. This phenomenon, called the optical Stark effect, is one of the promising candidates for realizing ultrafast optical switches. However, the ultrafast modulations induced by the coherent light-matter interactions usually involve unwanted incoherent responses, significantly reducing the overall operation speed. Here, by using ultrafast pump-probe spectroscopy, we suppress the incoherent response and modulate the coherent-to-incoherent ratio in the two-dimensional semiconductor ReS2. We selectively convert the coherent and incoherent responses of an anisotropic exciton state by solely using photon polarizations, improving the control ratio by 3 orders of magnitude. The efficient modulation was enabled by transient superpositions of differential spectra from two nondegenerate exciton states due to the light polarization dependencies. This work provides a valuable contribution toward realizing ideal ultrafast optical switches.

Analysis of Defect Recovery in Reduced Graphene Oxide and Its Application as a Heater for Self-Healing Polymers.

Reduced graphene oxide (RGO) obtained from graphene oxide has received much attention because of its simple and cost-effective manufacturing process. Previous studies have demonstrated the scalable production of RGO with relatively high quality; however, irreducible defects on RGO deteriorate the unique intrinsic physical properties of graphene, such as high-mobility electrical charge transport, limiting its potential applicability. Using the enhanced chemical reactivity of such defects, atomic layer deposition (ALD) can be a useful method to selectively passivate the defect sites. Herein, we analyzed the selective formation of Pt by ALD on the defect sites of RGO and investigated the effect of Pt formation on the electrical properties of RGO by using ultrafast terahertz (THz) laser spectroscopy. Time-resolved THz measurements directly corroborated that the degree of the defect-recovering property of ALD Pt-treated RGO appearing as Auger-type sub-picosecond relaxation, which is otherwise absent in pristine RGO. In addition, the conductivity improvement of Pt-recovered RGO was theoretically explained by density functional theory calculations. The ALD Pt-passivated RGO yielded a superior platform for the fabrication of a highly conductive and transparent graphene heater. By using the ALD Pt/RGO heater embedded underneath scratched self-healing polymer materials, we also demonstrated the effective recovery property of self-healing polymers with high-performance heating capability. Our work is expected to result in significant advances toward practical applications for RGO-based flexible and transparent electronics.

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High-Mobility MoS2 Field-Effect Transistors.

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post-silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high-performance devices while adapting for large-area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS2 devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD-grown MoS2 film and a Ag electrode as an interfacial layer. The MoS2 field-effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field-effect mobility of 35 cm2 V-1 s-1 , an on/off current ratio of 4 × 108 , and a photoresponsivity of 2160 A W-1 , compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n-doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS2 and electrodes. This demonstration of contact interface engineering with CVD-grown MoS2 and graphene is a key step toward the practical application of atomically thin TMDC-based devices with low-resistance contacts for high-performance large-area electronics and optoelectronics.

Time-Resolved Observations of Photo-Generated Charge-Carrier Dynamics in Sb2Se3 Photocathodes for Photoelectrochemical Water Splitting.

Solar-energy conversion by photoelectrochemical (PEC) devices is driven by the separation and transfer of photogenerated charge carriers. Thus, understanding carrier dynamics in a PEC device is essential to realizing efficient solar-energy conversion. Here, we investigate time-resolved carrier dynamics in emerging low-cost Sb2Se3 nanostructure photocathodes for PEC water splitting. Using terahertz spectroscopy, we observed an initial mobility loss within tens of picoseconds due to carrier localization and attributed the origin of carrier localization to the rich surface of Sb2Se3 nanostructures. In addition, a possible recombination at the interface between Sb2Se3 and the back contact is elucidated by time-resolved photoluminescence analysis. We also demonstrated the dual role of the RuO x co-catalyst in reducing surface recombination and enhancing charge transfer in full devices using intensity-modulated spectroscopy. The relatively low onset potential of the Sb2Se3 photocathode is attributed to the sluggish charge transfer at a low applied bias rather than to fast surface recombination. We believe that our insights on carrier dynamics would be an important step toward achieving highly efficient Sb2Se3 photocathodes.

Generation, transport and detection of valley-locked spin photocurrent in WSe2-graphene-Bi2Se3 heterostructures.

Quantum optoelectronic devices capable of isolating a target degree of freedom (DoF) from other DoFs have allowed for new applications in modern information technology. Many works on solid-state spintronics have focused on methods to disentangle the spin DoF from the charge DoF1, yet many related issues remain unresolved. Although the recent advent of atomically thin transition metal dichalcogenides (TMDs) has enabled the use of valley pseudospin as an alternative DoF2,3, it is nontrivial to separate the spin DoF from the valley DoF since the time-reversal valley DoF is intrinsically locked with the spin DoF4. Here, we demonstrate lateral TMD-graphene-topological insulator hetero-devices with the possibility of such a DoF-selective measurement. We generate the valley-locked spin DoF via a circular photogalvanic effect in an electric-double-layer WSe2 transistor. The valley-locked spin photocarriers then diffuse in a submicrometre-long graphene layer, and the spin DoF is measured separately in the topological insulator via non-local electrical detection using the characteristic spin-momentum locking. Operating at room temperature, our integrated devices exhibit a non-local spin polarization degree of higher than 0.5, providing the potential for coupled opto-spin-valleytronic applications that independently exploit the valley and spin DoFs.

Electrically Controllable Molecularization of Terahertz Meta-Atoms.

Active control of metamaterial properties is critical for advanced terahertz (THz) applications. However, the tunability of THz properties, such as the resonance frequency and phase of the wave, remains challenging. Here, a new device design is provided for extensively tuning the resonance properties of THz metamaterials. Unlike previous approaches, the design is intended to control the electrical interconnections between the metallic unit structures of metamaterials. This strategy is referred to as the molecularization of the meta-atoms and is accomplished by placing graphene bridges between the metallic unit structures whose conductivity is modulated by an electrolyte gating. Because of the scalable nature of the molecularization, the resonance frequency of the terahertz metamaterials can be tuned as a function of the number of meta-atoms constituting a unit metamolecule. At the same time, the voltage-controlled molecularization allows delicate control over the phase shift of the transmitted THz, without changing the high transmission of the materials significantly.

Publisher Correction: Ultrafast quantum beats of anisotropic excitons in atomically thin ReS2.

In the originally published HTML and PDF versions of this article, Figs. 3g and 4d contained typesetting errors affecting the way the data points were displayed. This has now been corrected in the HTML and PDF versions.

Control over Electron-Phonon Interaction by Dirac Plasmon Engineering in the Bi2Se3 Topological Insulator.

Understanding the mutual interaction between electronic excitations and lattice vibrations is key for understanding electronic transport and optoelectronic phenomena. Dynamic manipulation of such interaction is elusive because it requires varying the material composition on the atomic level. In turn, recent studies on topological insulators (TIs) have revealed the coexistence of a strong phonon resonance and topologically protected Dirac plasmon, both in the terahertz (THz) frequency range. Here, using these intrinsic characteristics of TIs, we demonstrate a new methodology for controlling electron-phonon interaction by lithographically engineered Dirac surface plasmons in the Bi2Se3 TI. Through a series of time-domain and time-resolved ultrafast THz measurements, we show that, when the Dirac plasmon energy is less than the TI phonon energy, the electron-phonon coupling is trivial, exhibiting phonon broadening associated with Landau damping. In contrast, when the Dirac plasmon energy exceeds that of the phonon resonance, we observe suppressed electron-phonon interaction leading to unexpected phonon stiffening. Time-dependent analysis of the Dirac plasmon behavior, phonon broadening, and phonon stiffening reveals a transition between the distinct dynamics corresponding to the two regimes as the Dirac plasmon resonance moves across the TI phonon resonance, which demonstrates the capability of Dirac plasmon control. Our results suggest that the engineering of Dirac plasmons provides a new alternative for controlling the dynamic interaction between Dirac carriers and phonons.

Ultrafast quantum beats of anisotropic excitons in atomically thin ReS2.

Quantum beats, periodic oscillations arising from coherent superposition states, have enabled exploration of novel coherent phenomena. Originating from strong Coulomb interactions and reduced dielectric screening, two-dimensional transition metal dichalcogenides exhibit strongly bound excitons either in a single structure or hetero-counterpart; however, quantum coherence between excitons is barely known to date. Here we observe exciton quantum beats in atomically thin ReS2 and further modulate the intensity of the quantum beats signal. Surprisingly, linearly polarized excitons behave like a coherently coupled three-level system exhibiting quantum beats, even though they exhibit anisotropic exciton orientations and optical selection rules. Theoretical studies are also provided to clarify that the observed quantum beats originate from pure quantum coherence, not from classical interference. Furthermore, we modulate on/off quantum beats only by laser polarization. This work provides an ideal laboratory toward polarization-controlled exciton quantum beats in two-dimensional materials.

Designing Two-Dimensional Dirac Heterointerfaces of Few-Layer Graphene and Tetradymite-Type Sb2Te3 for Thermoelectric Applications.

Despite the ubiquitous nature of the Peltier effect in low-dimensional thermoelectric devices, the influence of finite temperature on the electronic structure and transport in the Dirac heterointerfaces of the few-layer graphene and layered tetradymite, Sb2Te3 (which coincidently have excellent thermoelectric properties) are not well understood. In this work, using the first-principles density-functional theory calculations, we investigate the detailed atomic and electronic structure of these Dirac heterointerfaces of graphene and Sb2Te3 and further re-examine the effect of finite temperature on the electronic band structures using a phenomenological temperature-broadening model based on Fermi-Dirac statistics. We then proceed to understand the underlying charge redistribution process in this Dirac heterointerfaces and through solving the Boltzmann transport equation, we present the theoretical evidence of electron-hole asymmetry in its electrical conductivity as a consequence of this charge redistribution mechanism. We finally propose that the hexagonal-stacked Dirac heterointerfaces are useful as efficient p-n junction building blocks in the next-generation thermoelectric devices where the electron-hole asymmetry promotes the thermoelectric transport by "hot" excited charge carriers.

Sulfur vacancy-induced reversible doping of transition metal disulfides via hydrazine treatment.

Chemical doping of transition metal dichalcogenides (TMDCs) has drawn significant interest because of its applicability to the modification of electrical and optical properties of TMDCs. This is of fundamental and technological importance for high-efficiency electronic and optoelectronic devices. Here, we present a simple and facile route to reversible and controllable modulation of the electrical and optical properties of WS2 and MoS2via hydrazine doping and sulfur annealing. Hydrazine treatment of WS2 improves the field-effect mobilities, on/off current ratios, and photoresponsivities of the devices. This is due to the surface charge transfer doping of WS2 and the sulfur vacancies formed by its reduction, which result in an n-type doping effect. The changes in the electrical and optical properties are fully recovered when the WS2 is annealed in an atmosphere of sulfur. This method for reversible modulation can be applied to other transition metal disulfides including MoS2, which may enable the fabrication of two-dimensional electronic and optoelectronic devices with tunable properties and improved performance.