Non-epitaxial single-crystal 2D material growth by geometric confinement.

Two-dimensional (2D) materials and their heterostructures show a promising path for next-generation electronics1-3. Nevertheless, 2D-based electronics have not been commercialized, owing mainly to three critical challenges: i) precise kinetic control of layer-by-layer 2D material growth, ii) maintaining a single domain during the growth, and iii) wafer-scale controllability of layer numbers and crystallinity. Here we introduce a deterministic, confined-growth technique that can tackle these three issues simultaneously, thus obtaining wafer-scale single-domain 2D monolayer arrays and their heterostructures on arbitrary substrates. We geometrically confine the growth of the first set of nuclei by defining a selective growth area via patterning SiO2 masks on two-inch substrates. Owing to substantial reduction of the growth duration at the micrometre-scale SiO2 trenches, we obtain wafer-scale single-domain monolayer WSe2 arrays on the arbitrary substrates by filling the trenches via short growth of the first set of nuclei, before the second set of nuclei is introduced, thus without requiring epitaxial seeding. Further growth of transition metal dichalcogenides with the same principle yields the formation of single-domain MoS2/WSe2 heterostructures. Our achievement will lay a strong foundation for 2D materials to fit into industrial settings.

Dephasing Dynamics Accessed by High Harmonic Generation: Determination of Electron-Hole Decoherence of Dirac Fermions.

We reveal the critical effect of ultrashort dephasing on the polarization of high harmonic generation in Dirac fermions. As the elliptically polarized laser pulse falls in or slightly beyond the multiphoton regime, the elliptically polarized high harmonic generation is produced and exhibits a characteristic polarimetry of the polarization ellipse, which is found to depend on the decoherence time T2. T2 could then be determined to be a few femtoseconds directly from the experimentally observed polarimetry of high harmonics. This shows a sharp contrast with the semimetal regime of higher pump intensity, where the polarimetry is irrelevant to T2. An access to the dephasing dynamics would extend the prospect of high harmonic generation into the metrology of a femtosecond dynamic process in the coherent quantum control.

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.

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.

Gate-tunable quantum pathways of high harmonic generation in graphene.

Under strong laser fields, electrons in solids radiate high-harmonic fields by travelling through quantum pathways in Bloch bands in the sub-laser-cycle timescales. Understanding these pathways in the momentum space through the high-harmonic radiation can enable an all-optical ultrafast probe to observe coherent lightwave-driven processes and measure electronic structures as recently demonstrated for semiconductors. However, such demonstration has been largely limited for semimetals because the absence of the bandgap hinders an experimental characterization of the exact pathways. In this study, by combining electrostatic control of chemical potentials with HHG measurement, we resolve quantum pathways of massless Dirac fermions in graphene under strong laser fields. Electrical modulation of HHG reveals quantum interference between the multi-photon interband excitation channels. As the light-matter interaction deviates beyond the perturbative regime, elliptically polarized laser fields efficiently drive massless Dirac fermions via an intricate coupling between the interband and intraband transitions, which is corroborated by our theoretical calculations. Our findings pave the way for strong-laser-field tomography of Dirac electrons in various quantum semimetals and their ultrafast electronics with a gate control.

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.

Deep-ultraviolet electroluminescence and photocurrent generation in graphene/hBN/graphene heterostructures.

Hexagonal boron nitride (hBN) is a van der Waals semiconductor with a wide bandgap of ~ 5.96 eV. Despite the indirect bandgap characteristics of hBN, charge carriers excited by high energy electrons or photons efficiently emit luminescence at deep-ultraviolet (DUV) frequencies via strong electron-phonon interaction, suggesting potential DUV light emitting device applications. However, electroluminescence from hBN has not been demonstrated at DUV frequencies so far. In this study, we report DUV electroluminescence and photocurrent generation in graphene/hBN/graphene heterostructures at room temperature. Tunneling carrier injection from graphene electrodes into the band edges of hBN enables prominent electroluminescence at DUV frequencies. On the other hand, under DUV laser illumination and external bias voltage, graphene electrodes efficiently collect photo-excited carriers in hBN, which generates high photocurrent. Laser excitation micro-spectroscopy shows that the radiative recombination and photocarrier excitation processes in the heterostructures mainly originate from the pristine structure and the stacking faults in hBN. Our work provides a pathway toward efficient DUV light emitting and detection devices based on hBN.

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.

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.

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.

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.

1s-intraexcitonic dynamics in monolayer MoS2 probed by ultrafast mid-infrared spectroscopy.

The 1s exciton--the ground state of a bound electron-hole pair--is central to understanding the photoresponse of monolayer transition metal dichalcogenides. Above the 1s exciton, recent visible and near-infrared investigations have revealed that the excited excitons are much richer, exhibiting a series of Rydberg-like states. A natural question is then how the internal excitonic transitions are interrelated on photoexcitation. Accessing these intraexcitonic transitions, however, demands a fundamentally different experimental tool capable of probing optical transitions from 1s 'bright' to np 'dark' states. Here we employ ultrafast mid-infrared spectroscopy to explore the 1s intraexcitonic transitions in monolayer MoS2. We observed twofold 1s→3p intraexcitonic transitions within the A and B excitons and 1s→2p transition between the A and B excitons. Our results revealed that it takes about 0.7 ps for the 1s A exciton to reach quasi-equilibrium; a characteristic time that is associated with a rapid population transfer from the 1s B exciton, providing rich characteristics of many-body exciton dynamics in two-dimensional materials.

Selectively tunable optical Stark effect of anisotropic excitons in atomically thin ReS2.

The optical Stark effect is a coherent light-matter interaction describing the modification of quantum states by non-resonant light illumination in atoms, solids and nanostructures. Researchers have strived to utilize this effect to control exciton states, aiming to realize ultra-high-speed optical switches and modulators. However, most studies have focused on the optical Stark effect of only the lowest exciton state due to lack of energy selectivity, resulting in low degree-of-freedom devices. Here, by applying a linearly polarized laser pulse to few-layer ReS2, where reduced symmetry leads to strong in-plane anisotropy of excitons, we control the optical Stark shift of two energetically separated exciton states. Especially, we selectively tune the Stark effect of an individual state with varying light polarization. This is possible because each state has a completely distinct dependence on light polarization due to different excitonic transition dipole moments. Our finding provides a methodology for energy-selective control of exciton states.

Solvent-Assisted Gel Printing for Micropatterning Thin Organic-Inorganic Hybrid Perovskite Films.

While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems.

Unusually efficient photocurrent extraction in monolayer van der Waals heterostructure by tunnelling through discretized barriers.

Two-dimensional layered transition-metal dichalcogenides have attracted considerable interest for their unique layer-number-dependent properties. In particular, vertical integration of these two-dimensional crystals to form van der Waals heterostructures can open up a new dimension for the design of functional electronic and optoelectronic devices. Here we report the layer-number-dependent photocurrent generation in graphene/MoS2/graphene heterostructures by creating a device with two distinct regions containing one-layer and seven-layer MoS2 to exclude other extrinsic factors. Photoresponse studies reveal that photoresponsivity in one-layer MoS2 is surprisingly higher than that in seven-layer MoS2 by seven times. Spectral-dependent studies further show that the internal quantum efficiency in one-layer MoS2 can reach a maximum of 65%, far higher than the 7% in seven-layer MoS2. Our theoretical modelling shows that asymmetric potential barriers in the top and bottom interfaces of the graphene/one-layer MoS2/graphene heterojunction enable asymmetric carrier tunnelling, to generate usually high photoresponsivity in one-layer MoS2 device.

Rotation-misfit-free heteroepitaxial stacking and stitching growth of hexagonal transition-metal dichalcogenide monolayers by nucleation kinetics controls.

2D vertical stacking and lateral stitching growth of monolayer (ML) hexagonal transition-metal dichalcogenides are reported. The 2D heteroepitaxial manipulation of MoS2 and WS2 MLs is achieved by control of the 2D nucleation kinetics during the sequential vapor-phase growth. It enables the creation of hexagon-on-hexagon unit-cell stacking and hexagon-by-hexagon stitching without interlayer rotation misfits.

Ultra-high modulation depth exceeding 2,400% in optically controlled topological surface plasmons.

Modulating light via coherent charge oscillations in solids is the subject of intense research topics in opto-plasmonics. Although a variety of methods are proposed to increase such modulation efficiency, one central challenge is to achieve a high modulation depth (defined by a ratio of extinction with/without light) under small photon-flux injection, which becomes a fundamental trade-off issue both in metals and semiconductors. Here, by fabricating simple micro-ribbon arrays of topological insulator Bi2Se3, we report an unprecedentedly large modulation depth of 2,400% at 1.5 THz with very low optical fluence of 45 µJ cm(-2). This was possible, first because the extinction spectrum is nearly zero due to the Fano-like plasmon-phonon-destructive interference, thereby contributing an extremely small denominator to the extinction ratio. Second, the numerator of the extinction ratio is markedly increased due to the photoinduced formation of massive two-dimensional electron gas below the topological surface states, which is another contributor to the ultra-high modulation depth.

Interlayer orientation-dependent light absorption and emission in monolayer semiconductor stacks.

Two-dimensional stacks of dissimilar hexagonal monolayers exhibit unusual electronic, photonic and photovoltaic responses that arise from substantial interlayer excitations. Interband excitation phenomena in individual hexagonal monolayer occur in states at band edges (valleys) in the hexagonal momentum space; therefore, low-energy interlayer excitation in the hexagonal monolayer stacks can be directed by the two-dimensional rotational degree of each monolayer crystal. However, this rotation-dependent excitation is largely unknown, due to lack in control over the relative monolayer rotations, thereby leading to momentum-mismatched interlayer excitations. Here, we report that light absorption and emission in MoS2/WS2 monolayer stacks can be tunable from indirect- to direct-gap transitions in both spectral and dynamic characteristics, when the constituent monolayer crystals are coherently stacked without in-plane rotation misfit. Our study suggests that the interlayer rotational attributes determine tunable interlayer excitation as a new set of basis for investigating optical phenomena in a two-dimensional hexagonal monolayer system.

Flexible transition metal dichalcogenide nanosheets for band-selective photodetection.

The photocurrent conversions of transition metal dichalcogenide nanosheets are unprecedentedly impressive, making them great candidates for visible range photodetectors. Here we demonstrate a method for fabricating micron-thick, flexible films consisting of a variety of highly separated transition metal dichalcogenide nanosheets for excellent band-selective photodetection. Our method is based on the non-destructive modification of transition metal dichalcogenide sheets with amine-terminated polymers. The universal interaction between amine and transition metal resulted in scalable, stable and high concentration dispersions of a single to a few layers of numerous transition metal dichalcogenides. Our MoSe2 and MoS2 composites are highly photoconductive even at bending radii as low as 200 µm on illumination of near infrared and visible light, respectively. More interestingly, simple solution mixing of MoSe2 and MoS2 gives rise to blended composite films in which the photodetection properties were controllable. The MoS2/MoSe2 (5:5) film showed broad range photodetection suitable for both visible and near infrared spectra.