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.

Science of 2.5 dimensional materials: paradigm shift of materials science toward future social innovation.

The past decades of materials science discoveries are the basis of our present society - from the foundation of semiconductor devices to the recent development of internet of things (IoT) technologies. These materials science developments have depended mainly on control of rigid chemical bonds, such as covalent and ionic bonds, in organic molecules and polymers, inorganic crystals and thin films. The recent discovery of graphene and other two-dimensional (2D) materials offers a novel approach to synthesizing materials by controlling their weak out-of-plane van der Waals (vdW) interactions. Artificial stacks of different types of 2D materials are a novel concept in materials synthesis, with the stacks not limited by rigid chemical bonds nor by lattice constants. This offers plenty of opportunities to explore new physics, chemistry, and engineering. An often-overlooked characteristic of vdW stacks is the well-defined 2D nanospace between the layers, which provides unique physical phenomena and a rich field for synthesis of novel materials. Applying the science of intercalation compounds to 2D materials provides new insights and expectations about the use of the vdW nanospace. We call this nascent field of science '2.5 dimensional (2.5D) materials,' to acknowledge the important extra degree of freedom beyond 2D materials. 2.5D materials not only offer a new field of scientific research, but also contribute to the development of practical applications, and will lead to future social innovation. In this paper, we introduce the new scientific concept of this science of '2.5D materials' and review recent research developments based on this new scientific concept.

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.

Carbon Nanotube Photoluminescence Modulation by Local Chemical and Supramolecular Chemical Functionalization.

ConspectusCarbon nanotubes (CNTs) have been central materials in nanoscience and nanotechnologies. Single-walled CNTs (SWCNTs) consisting of a cylindrical graphene show a metallic (met) or semiconducting (sc) property depending on their rolling up manner (chirality). The sc-SWCNTs show characteristic chirality-dependent optical properties of their absorption and photoluminescence (PL) in the near-infrared (NIR) region. These are derived from their highly π-conjugated structures having semiconducting crystalline sp2 carbon networks with defined nanoarchitectures that afford a strong quantum confinement and weak dielectric screening. Consequently, photoirradiation of the SWCNTs produces a stable and mobile exciton (excited electron-hole pair) even at room temperature, and the exciton properties dominate such optical phenomena in the SWCNTs. However, the mobile excitons decrease the PL efficiency due to nonradiative relaxation including collision with tube edges and relaxation to lower-lying dark states. A breakthrough regarding the efficient use of the mobile exciton for PL has recently been achieved by local chemical functionalization of the SWCNTs, in which the chemical reactions introduce local defects of oxygen and sp3 carbon atoms in the tube structures. The defect doping creates new emissive doped sites that have narrower band gaps and trap the mobile excitons, which provides locally functionalized SWCNTs (lf-SWCNTs). As a result, the localized exciton produces E11* PL with red-shifted wavelengths and enhanced PL quantum yields compared to the original E11 PL of the nonmodified SWCNTs.In this Account, we describe recently revealed fundamental properties of the lf-SWCNTs based on the analyses by photophysics, theoretical calculations, and electrochemistry combined with in situ PL spectroscopy. The new insight allows us to expand the wavelength regions of the NIR E11* PL derived from the localized exciton, in which upconversion generates a higher energy PL through thermal activation and proximal doped site formation using bis-aryldiazonium modifiers provides a much lower energy PL than typical E11* PL. Moreover, owing to the chemical reaction-dominant doping process, the molecular structure design of modifiers succeeds in producing functionalized lf-SWCNTs; namely, molecular functions are incorporated into the doped sites for their PL modulation. The wavelength changes/switching in the E11* PL selectively occurs by a supramolecular approach using molecular recognition and imine chemistry. Therefore, the local chemical functionalization of the SWCNTs is a key to designing the properties and creating their new functions of the lf-SWCNTs. Fundamental understanding of the doped site properties of the lf-SWCNTs and molecularly driven approaches for exciton and defect engineering would unveil the intrinsic natures of these materials, which is crucial for elevating the SWCNT-based nanotechnologies to the next stage. The resulting materials are of interest in the fields of high performance NIR-II imaging and sensing for bio/medical analyses and single-photon emitters in quantum information technology.

Tuning the Reactivity of a Substrate for SNAP-Tag Expands Its Application for Recognition-Driven DNA-Protein Conjugation.

Recognition-driven modification has been emerging as a novel approach to modifying biomolecular targets of interest site-specifically and efficiently. To this end, protein modular adaptors (MAs) are the ideal reaction model for recognition-driven modification of DNA as they consist of both a sequence-specific DNA-binding domain (DBD) and a self-ligating protein-tag. Coupling DNA recognition by DBD and the chemoselective reaction of the protein tag could provide a highly efficient sequence-specific reaction. However, combining an MA consisting of a reactive protein-tag and its substrate, for example, SNAP-tag and benzyl guanine (BG), revealed rather nonselective reaction with DNA. Therefore new substrates of SNAP-tag have been designed to realize sequence-selective rapid crosslinking reactions of MAs with SNAP-tag. The reactions of substrates with SNAP-tag were verified by kinetic analyses to enable the sequence-selective crosslinking reaction of MA. The new substrate enables the distinctive orthogonality of SNAP-tag against CLIP-tag to achieve orthogonal DNA-protein crosslinking by six unique MAs.

Analgesic Mechanisms of Steroid Ointment against Oral Ulcerative Mucositis in a Rat Model.

Despite the long history of use of steroid ointments for oral mucositis, the analgesic mechanism has not been fully elucidated. In this study, we examined the effects of triamcinolone acetonide (Tmc) on oral ulcerative mucositis-induced pain in conscious rats by our proprietary assay system. Based on evaluations of the physical properties and retention periods in the oral mucosa of human volunteers and rats, we selected TRAFUL® ointment as a long-lasting base. In oral ulcerative mucositis model rats, TRAFUL® with Tmc suppressed cyclooxygenase-dependent inflammatory responses with upregulations of glucocorticoid receptor-induced anti-inflammatory genes and inhibited spontaneous nociceptive behavior. When an ointment with a shorter residual period was used, the effects of Tmc were not elicited or were induced to a lesser extent. Importantly, TRAFUL® with Tmc also improved oral ulcerative mucositis-induced mechanical allodynia, which has been reported to be independent of cyclooxygenase. Ca2+ imaging in dissociated trigeminal ganglion neurons showed that long-term preincubation with Tmc inhibited the hypertonic stimulation-induced Ca2+ response. These results suggest that the representative steroid Tmc suppresses oral ulcerative mucositis-induced pain by general anti-inflammatory actions and inhibits mechanical sensitivity in peripheral nerves. For drug delivery, long-lasting ointments such as TRAFUL® are needed to sufficiently induce the therapeutic effects.

ChIP-seq analysis of genomic binding regions of five major transcription factors highlights a central role for ZIC2 in the mouse epiblast stem cell gene regulatory network.

To obtain insight into the transcription factor (TF)-dependent regulation of epiblast stem cells (EpiSCs), we performed ChIP-seq analysis of the genomic binding regions of five major TFs. Analysis of in vivo biotinylated ZIC2, OTX2, SOX2, POU5F1 and POU3F1 binding in EpiSCs identified several new features. (1) Megabase-scale genomic domains rich in ZIC2 peaks and genes alternate with those rich in POU3F1 but sparse in genes, reflecting the clustering of regulatory regions that act at short and long-range, which involve binding of ZIC2 and POU3F1, respectively. (2) The enhancers bound by ZIC2 and OTX2 prominently regulate TF genes in EpiSCs. (3) The binding sites for SOX2 and POU5F1 in mouse embryonic stem cells (ESCs) and EpiSCs are divergent, reflecting the shift in the major acting TFs from SOX2/POU5F1 in ESCs to OTX2/ZIC2 in EpiSCs. (4) This shift in the major acting TFs appears to be primed by binding of ZIC2 in ESCs at relevant genomic positions that later function as enhancers following the disengagement of SOX2/POU5F1 from major regulatory functions and subsequent binding by OTX2. These new insights into EpiSC gene regulatory networks gained from this study are highly relevant to early stage embryogenesis.

Observation of Drastic Electronic-Structure Change in a One-Dimensional Moiré Superlattice.

We report the first experimental observation of a strong-coupling effect in a one-dimensional moiré superlattice. We study one-dimensional double-wall carbon nanotubes (DWCNTs) in which van der Waals-coupled two single nanotubes form a one-dimensional moiré superlattice. We experimentally combine Rayleigh scattering spectroscopy and electron beam diffraction on the same individual DWCNTs to probe the optical transitions of the structure-identified DWCNTs in the visible spectral range. Among more than 30 structure-identified DWCNTs examined, we experimentally observed and identified a drastic change of the optical transition spectrum in a DWCNT with chirality (12,11)@(17,16). The origin of the marked change is attributed to the strong intertube coupling effect in the moiré superlattice formed by two nearly armchair nanotubes. Our numerical simulation is consistent with the experimental findings.

Effect of tranexamic acid in improving the lifespan of naturally aging mice.

An effective method to improve lifespan is not known. Therefore, in this study, we examined the lifespan-extending effect of tranexamic acid in normal mice. We bred hairless mice without exposure to ultraviolet radiation and psychical stress until they died naturally. During the study period, the mice were orally administered tranexamic acid (12 mg/kg/day) three times weekly. An increase in the lifespan of mice was observed by tranexamic acid administration. Furthermore, age-related diseases of the skin were ameliorated by tranexamic acid administration. Moreover, the blood level of tumor necrosis factor-α, interleukin-6, reactive oxygen species (ROS), and matrix metalloproteinase (MMP)-9 was decreased by tranexamic acid administration. These results indicate that tranexamic acid suppresses the secretion of inflammatory cytokines, MMP-9, and ROS induced by natural aging, ameliorating age-related diseases, and, consequently, extending the lifespan.

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.

Cooperation of Sall4 and Sox8 transcription factors in the regulation of the chicken Sox3 gene during otic placode development.

To elucidate the transcriptional regulation that underlies specification of the otic placode, we investigated the Sox3 downstream enhancer Otic1 of the chicken, the activity of which is restricted to and distributed across the entire otic placode. The 181-bp Otic1 enhancer sequence was dissected into a 68-bp minimal activating sequence, which exhibited dimer enhancer activity in the otic placode and cephalic neural crest, and this was further reduced to a 25-bp Otic1 core sequence, which also showed octamer enhancer activity in the same regions. The Otic1 core octamer was activated by the combined action of Sall4 and the SoxE transcription factors (TFs) Sox8 or Sox9. Binding of Sall4, Sox8 and Sox9 to the Otic1 sequence in embryonic tissues was confirmed by ChIP-qPCR analysis. The core-adjoining 3' side sequences of Otic1 augmented its enhancer activity, while inclusion of the CAGGTG sequence in the immediate 3' end of the 68-bp sequence repressed its enhancer activity outside the otic placode. The CAGGTG sequence likely serves as the binding sites of the repressor TFs δEF1 (Zeb1), Sip1 (Zeb2), and Snail2, all of which are expressed in the cephalic neural crest but not in the otic placode. Therefore, the combination of Sall4-Sox8-dependent activation and CAGGTG sequence-dependent repression determines otic placode development. Although the Otic1 sequence is not conserved in mammals or fishes, the activation mechanism is, as Otic1 was also activated in otic placode tissues developed from mouse embryonic stem cells and transient transgenic zebrafish embryos.

van der Waals interaction-induced photoluminescence weakening and multilayer growth in epitaxially aligned WS2.

Recently, transition metal dichalcogenides (TMDCs) have attracted great interest due to their unique electronic and optical properties. Chemical vapor deposition (CVD) has been regarded as the most promising method for the synthesis of large-area TMDCs with high reproducibility. Having similar hexagonal crystal structures with many TMDCs, c-plane sapphire is commonly used as a growth substrate in CVD. However, few studies have been reported on the influence of the sapphire substrate on the growth behavior and physical properties of TMDCs. In this work, we demonstrate that higher strain is induced in epitaxially grown WS2 grains via van der Waals interactions with sapphire as compared with misaligned WS2 grains. In addition, this strain was found to enhance overlayer deposition on monolayer WS2, while multilayer growth was not observed in non-epitaxial WS2. Photoluminescence (PL) of the epitaxially grown WS2 grains was reduced, reflecting the effective van der Waals interaction with sapphire. Moreover, low-temperature PL measurements revealed strong influence of the c-plane sapphire surface on the optical properties of WS2. Density functional theory (DFT) calculation supports that the aligned WS2 grains are more strongly bound to the sapphire surface, as compared with misaligned WS2. Our work offers a new insight into the understanding of the influence of the substrate on the CVD-grown TMDC materials.

Evidence for Fast Interlayer Energy Transfer in MoSe2/WS2 Heterostructures.

Strongly bound excitons confined in two-dimensional (2D) semiconductors are dipoles with a perfect in-plane orientation. In a vertical stack of semiconducting 2D crystals, such in-plane excitonic dipoles are expected to efficiently couple across van der Waals gap due to strong interlayer Coulomb interaction and exchange their energy. However, previous studies on heterobilayers of group 6 transition metal dichalcogenides (TMDs) found that the exciton decay dynamics is dominated by interlayer charge transfer (CT) processes. Here, we report an experimental observation of fast interlayer energy transfer (ET) in MoSe2/WS2 heterostructures using photoluminescence excitation (PLE) spectroscopy. The temperature dependence of the transfer rates suggests that the ET is Förster-type involving excitons in the WS2 layer resonantly exciting higher-order excitons in the MoSe2 layer. The estimated ET time of the order of 1 ps is among the fastest compared to those reported for other nanostructure hybrid systems such as carbon nanotube bundles. Efficient ET in these systems offers prospects for optical amplification and energy harvesting through intelligent layer engineering.

Transcriptional regulatory networks in epiblast cells and during anterior neural plate development as modeled in epiblast stem cells.

Somatic development initiates from the epiblast in post-implantation mammalian embryos. Recent establishment of epiblast stem cell (EpiSC) lines has opened up new avenues of investigation of the mechanisms that regulate the epiblast state and initiate lineage-specific somatic development. Here, we investigated the role of cell-intrinsic core transcriptional regulation in the epiblast and during derivation of the anterior neural plate (ANP) using a mouse EpiSC model. Cells that developed from EpiSCs in one day in the absence of extrinsic signals were found to represent the ANP of ~E7.5 embryos. We focused on transcription factors that are uniformly expressed in the E6.5 epiblast but in a localized fashion within or external to the ANP at E7.5, as these are likely to regulate the epiblast state and ANP development depending on their balance. Analyses of the effects of knockdown and overexpression of these factors in EpiSCs on the levels of downstream transcription factors identified the following regulatory functions: cross-regulation among Zic, Otx2, Sox2 and Pou factors stabilizes the epiblastic state; Zic, Otx2 and Pou factors in combination repress mesodermal development; Zic and Sox2 factors repress endodermal development; and Otx2 represses posterior neural plate development. All of these factors variably activate genes responsible for neural plate development. The direct interaction of these factors with enhancers of Otx2, Hesx1 and Sox2 genes was demonstrated. Thus, a combination of regulatory processes that suppresses non-ANP lineages and promotes neural plate development determines the ANP.

Dkk1-dependent inhibition of Wnt signaling activates Hesx1 expression through its 5' enhancer and directs forebrain precursor development.

Development of the anterior forebrain precursor (AFBP) in the anterior neural plate (ANP) depends on the activation of the Hesx1 transcription factor gene. The Hesx1-expression domain of the ANP is underlain by Dkk1-expressing tissues, initially proximal-most anterior visceral endoderm (AVE), and later anterior mesendoderm (AME). As Dkk1-null embryos fail to develop the Hesx1-expressing domain, it is likely that Wnt signal inhibition in the ANP is required for the Hesx1 activation. To investigate the regulation of the AFBP development, we took advantage of epiblast stem cells (EpiSCs), which develop into the ANP in the absence of activin signaling. Expression of Hesx1 and Six3, both involved in the AFBP development, was strongly activated 2 days after activin removal and concomitant addition of Wnt signal inhibitors, Dkk1 or XAV939. Furthermore, we showed that activation of the 720-bp Hesx1 5' enhancer is responsible for Hesx1 expression in the AFBP and depends on Wnt signal inhibition. In addition, we showed that Wnt inhibition during the first day has larger impact on the activation of Hesx1 and Six3 than the second day, suggesting that in embryos Wnt inhibition caused by the AVE-derived Dkk1, rather than the AME-derived Dkk1, contributes greatly in the establishment of the AFBP.

Tunable photoluminescence of monolayer MoS2 via chemical doping.

We demonstrate the tunability of the photoluminescence (PL) properties of monolayer (1L)-MoS2 via chemical doping. The PL intensity of 1L-MoS2 was drastically enhanced by the adsorption of p-type dopants with high electron affinity but reduced by the adsorption of n-type dopants. This PL modulation results from switching between exciton PL and trion PL depending on carrier density in 1L-MoS2. Achievement of the extraction and injection of carriers in 1L-MoS2 by this solution-based chemical doping method enables convenient control of optical and electrical properties of atomically thin MoS2.

Quantum coherence and interference of a single moiré exciton in nano-fabricated twisted monolayer semiconductor heterobilayers.

The moiré potential serves as a periodic quantum confinement for optically generated excitons, creating spatially ordered zero-dimensional quantum systems. However, a broad emission spectrum resulting from inhomogeneity among moiré potentials hinders the investigation of their intrinsic properties. In this study, we demonstrated a method for the optical observation of quantum coherence and interference of a single moiré exciton in a twisted semiconducting heterobilayer beyond the diffraction limit of light. We observed a single and sharp photoluminescence peak from a single moiré exciton following nanofabrication. Our findings revealed the extended duration of quantum coherence in a single moiré exciton, persisting beyond 10 ps, and an accelerated decoherence process with increasing temperature and excitation power density. Moreover, quantum interference experiments revealed the coupling between moiré excitons in different moiré potential minima. The observed quantum coherence and interference of moiré exciton will facilitate potential applications of moiré quantum systems in quantum technologies.

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.

High-throughput dry transfer and excitonic properties of twisted bilayers based on CVD-grown transition metal dichalcogenides.

van der Waals (vdW) layered materials have attracted much attention because their physical properties can be controlled by varying the twist angle and layer composition. However, such twisted vdW assemblies are often prepared using mechanically exfoliated monolayer flakes with unintended shapes through a time-consuming search for such materials. Here, we report the rapid and dry fabrication of twisted multilayers using chemical vapor deposition (CVD) grown transition metal chalcogenide (TMDC) monolayers. By improving the adhesion of an acrylic resin stamp to the monolayers, the single crystals of various TMDC monolayers with desired grain size and density on a SiO2/Si substrate can be efficiently picked up. The present dry transfer process demonstrates the one-step fabrication of more than 100 twisted bilayers and the sequential stacking of a twisted 10-layer MoS2 single crystal. Furthermore, we also fabricated hBN-encapsulated TMDC monolayers and various twisted bilayers including MoSe2/MoS2, MoSe2/WSe2, and MoSe2/WS2. The interlayer interaction and quality of dry-transferred, CVD-grown TMDCs were characterized by using photoluminescence (PL), cathodoluminescence (CL) spectroscopy, and cross-sectional electron microscopy. The prominent PL peaks of interlayer excitons can be observed for MoSe2/MoS2 and MoSe2/WSe2 with small twist angles at room temperature. We also found that the optical spectra were locally modulated due to nanosized bubbles, which are formed by the presence of interface carbon impurities. The present findings indicate the widely applicable potential of the present method and enable an efficient search of the emergent optical and electrical properties of TMDC-based vdW heterostructures.