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We have previously shown that nano-sized graphene oxide (NGO) displays anti-inflammatory activities against natural killer T (NKT) cell-mediated sepsis. To address whether NGO could be applied to treat acute skin inflammation we developed a conventional skin Cetaphil® cream containing NGO (NGO cream) for topical application to skin lesions and investigated its therapeutic efficacy by employing the tape-stripping-induced acute skin inflammation model. Topical application of NGO cream to the wounded area significantly reduced skin lesions compared with the control cream. Moreover, NGO cream treatment prevented the tape-stripping-elicited infiltration of and IL1β production by skin neutrophils and dendritic cells (DCs). Furthermore, such anti-inflammatory effects of NGO cream were attributed to decreased infiltration of IL12-producing DCs and IFNγ-producing cells (e.g., CD4 + T, CD8 + T, γδ T, NK, and NKT cells) into the skin. In addition, topical NGO cream administration enhanced the expression of suppressive molecules such as FR4 on skin regulatory T cells. Through RNA sequencing analysis, we found that the preventive effect of NGO cream on acute skin inflammation may be correlated with the activation of keratinocytes located in the epidermis. Our results support NGO cream as a therapeutic option to control acute skin inflammation., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Graphene oxide (GO), a carbon-based material with oxygen-containing functional groups, can be applied in biomedicine for drug delivery, cancer therapy, and tissue regeneration. We have previously shown that nanoscale-sized graphene oxide (NGO), an oxidized graphene derivative, exhibits effective anti-inflammatory activity in a murine model of sepsis mediated by T helper (Th)1-promoting cytokines such as IFNγ and TNFα. However, whether NGO influences Th2-induced skin inflammation remains unclear. To address this issue, we employed an ovalbumin (OVA) plus aluminum hydroxide (Alum)-induced Th2-mediated skin inflammation model in conjunction with OVA-specific DO11.10 T cell receptor transgenic Balb/c mice. In vivo NGO injection upon OVA/Alum sensitization down-regulated OVA-elicited antigen-specific Th2 cells and GATA3-expressing Th2-type regulatory T cells. Next, we examined the effect of NGO injection on OVA/Alum-induced atopic dermatitis (AD)-like skin inflammation. NGO-injected mice exhibited significantly decreased Th2 disease phenotypes (e.g., a lower clinical score, decreased epidermal thickness and Th2 cell differentiation, and fewer infiltrated mast cells and basophils in skin lesions) compared with vehicle-injected control mice. Overall, our results suggest that NGOs are promising therapeutic materials for treating allergic diseases such as AD.

Two-dimensional (2D) materials have shown outstanding potential for new devices based on their interesting electrical properties beyond conventional 3D materials. In recent years, new concepts such as the valley degree of freedom have been studied to develop valleytronics in hexagonal lattice 2D materials. We investigated the valley degree of freedom of GaX and Janus GaXY (X, Y = S, Se, Te). By considering the spin-orbit coupling (SOC) effect in the band structure calculations, we identified the Rashba-type spin splitting in band structures of Janus Ga 2 SSe and Ga 2 STe. Further, we confirmed that the Zeeman-type spin splitting at the K and K' valleys of GaX and Janus Ga 2 XY show opposite spin contributions. We also calculated the Berry curvatures of GaX and Janus GaXY. In this study, we find that GaX and Janus Ga 2 XY have a similar magnitude of Berry curvatures, while having opposite signs at the K and K' points. In particular, GaTe and Ga 2 SeTe have relatively larger Berry curvatures of about 3.98 Å 2 and 3.41 Å 2 , respectively, than other GaX and Janus Ga 2 XY.

Two-dimensional (2D) vertical van der Waals heterostructures (vdWHs) show great potential across various applications. However, synthesizing large-scale structures poses challenges owing to the intricate growth parameters, forming unexpected hybrid film structures. Thus, precision in synthesis and thorough structural analysis are essential aspects. In this study, we successfully synthesized large-scale structured 2D transition metal dichalcogenides (TMDs) via chemical vapor deposition using metal oxide (WO 3 and MoO 3 ) thin films and a diluted H 2 S precursor, individual MoS 2 , WS 2 films and various MoS 2 /WS 2 hybrid films (Type I: Mo x W 1-x S 2 alloy; Type II: MoS 2 /WS 2 vdWH; Type III: MoS 2 dots/WS 2 ). Structural analyses, including optical microscopy, Raman spectroscopy, transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy, and cross-sectional imaging revealed that the A 1g and E 2g modes of WS 2 and MoS 2 were sensitive to structural variations, enabling hybrid structure differentiation. Type II showed minimal changes in the MoS 2' s A 1g mode, while Types I and III exhibited a ~2.8 cm -1 blue shift. Furthermore, the A 1g mode of WS 2 in Type I displayed a 1.4 cm -1 red shift. These variations agreed with the TEM-observed microstructural features, demonstrating strain effects on the MoS 2 -WS 2 interfaces. Our study provides insights into the structural features of diverse hybrid TMD materials, facilitating their differentiation through Raman spectroscopy.

In this study, we investigate the thermochemical stability of graphene on the GaN substrate for metal-organic chemical vapor deposition (MOCVD)-based remote epitaxy. Despite excellent physical properties of GaN, making it a compelling choice for high-performance electronic and light-emitting device applications, the challenge of thermochemical decomposition of graphene on a GaN substrate at high temperatures has obstructed the achievement of remote homoepitaxy via MOCVD. Our research uncovers an unexpected stability of graphene on N-polar GaN, thereby enabling the MOCVD-based remote homoepitaxy of N-polar GaN. Our comparative analysis of N- and Ga-polar GaN substrates reveals markedly different outcomes: while a graphene/N-polar GaN substrate produces releasable microcrystals (μCs), a graphene/Ga-polar GaN substrate yields nonreleasable thin films. We attribute this discrepancy to the polarity-dependent thermochemical stability of graphene on the GaN substrate and its subsequent reaction with hydrogen. Evidence obtained from Raman spectroscopy, electron microscopic analyses, and overlayer delamination points to a pronounced thermochemical stability of graphene on N-polar GaN during MOCVD-based remote homoepitaxy. Molecular dynamics simulations, corroborated by experimental data, further substantiate that the thermochemical stability of graphene is reliant on the polarity of GaN, due to different reactions with hydrogen at high temperatures. Based on the N-polar remote homoepitaxy of μCs, the practical application of our findings was demonstrated in fabrication of flexible light-emitting diodes composed of p-n junction μCs with InGaN heterostructures.

We report on the covalent binding of acetonitrile (CH 3 CN) on Si{111}-(7 × 7) at ∼300 K studied by scanning tunneling microscopy, thermal desorption spectroscopy, and first-principles theoretical calculations. The site-specific study makes it possible to unravel the site-by-site and step-by-step kinetics. A polarized CH 3 CN prefers to adsorb on the faulted half more frequently compared to on the unfaulted half. Moreover, a molecular CH 3 CN adsorbs four-times more preferably on the center adatom-rest atom (CEA-REA) pair than on the corner adatom-rest atom (COA-REA) pair. Such site selectivity, the number ratio of reacted-CEA/reacted-COA, depends on the number of reacted adatoms in the half-unit cell. The site selectivity and the resulting reacted-adatom patterns are understood well by considering a simple model. In this simple model, the molecular adsorption probability changes step-by-step and site-by-site with increasing reacted adatoms. Furthermore, our theoretical calculations are overall consistent with the experimental results. The site-selectivity of the adsorption of CH 3 CN on Si{111}-(7 × 7) is explained well by the chemical reactivity depending on the local conformation, the local density of states, and the interaction between polarized adsorbates., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Layer transfer techniques have been extensively explored for semiconductor device fabrication as a path to reduce costs and to form heterogeneously integrated devices. These techniques entail isolating epitaxial layers from an expensive donor wafer to form freestanding membranes. However, current layer transfer processes are still low-throughput and too expensive to be commercially suitable. Here we report a high-throughput layer transfer technique that can produce multiple compound semiconductor membranes from a single wafer. We directly grow two-dimensional (2D) materials on III-N and III-V substrates using epitaxy tools, which enables a scheme comprised of multiple alternating layers of 2D materials and epilayers that can be formed by a single growth run. Each epilayer in the multistack structure is then harvested by layer-by-layer mechanical exfoliation, producing multiple freestanding membranes from a single wafer without involving time-consuming processes such as sacrificial layer etching or wafer polishing. Moreover, atomic-precision exfoliation at the 2D interface allows for the recycling of the wafers for subsequent membrane production, with the potential for greatly reducing the manufacturing cost., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

Group IV monochalcogenides have recently shown great potential for their thermoelectric, ferroelectric, and other intriguing properties. The electrical properties of group IV monochalcogenides exhibit a strong dependence on the chalcogen type. For example, GeTe exhibits high doping concentration, whereas S/Se-based chalcogenides are semiconductors with sizable bandgaps. Here, we investigate the electrical and thermoelectric properties of γ-GeSe, a recently identified polymorph of GeSe. γ-GeSe exhibits high electrical conductivity (∼10 6 S/m) and a relatively low Seebeck coefficient (9.4 μV/K at room temperature) owing to its high p-doping level (5 × 10 21 cm -3 ), which is in stark contrast to other known GeSe polymorphs. Elemental analysis and first-principles calculations confirm that the abundant formation of Ge vacancies leads to the high p-doping concentration. The magnetoresistance measurements also reveal weak antilocalization because of spin-orbit coupling in the crystal. Our results demonstrate that γ-GeSe is a unique polymorph in which the modified local bonding configuration leads to substantially different physical properties.

Using density functional theory calculations, atomic and electronic structure of defects in monolayer GeS were investigated by focusing on the effects of vacancies and substitutional atoms. We chose group IV or chalcogen elements as substitutional ones, which substitute for Ge or S in GeS. It was found that the bandgap of GeS with substitutional atoms is close to that of pristine GeS, while the bandgap of GeS with Ge or S vacancies was smaller than that of pristine GeS. In terms of formation energy, monolayer GeS with Ge vacancies is more stable than that with S vacancies, and notably GeS with Ge substituted with Sn is most favorable within the range of chemical potential considered. Defects affect the piezoelectric properties depending on vacancies or substitutional atoms. Especially, GeS with substitutional atoms has almost the same piezoelectric stress coefficients eij as pristine GeS while having lower piezoelectric strain coefficients dij  but still much higher than other 2D materials. It is therefore concluded that Sn can effectively heal Ge vacancy in GeS, keeping high piezoelectric strain coefficients.

The electrical phase transition in van der Waals (vdW) layered materials such as transition-metal dichalcogenides and Bi 2 Sr 2 CaCu 2 O 8+x (Bi-2212) high-temperature superconductor has been explored using various techniques, including scanning tunneling and photoemission spectroscopies, and measurements of electrical resistance as a function of temperature. In this study, we develop one useful method to elucidate the electrical phases in vdW layered materials: indium (In)-contacted vdW tunneling spectroscopy for 1T-TaS 2 , Bi-2212 and 2H-MoS 2 . We utilized the vdW gap formed at an In/vdW material interface as a tunnel barrier for tunneling spectroscopy. For strongly correlated electron systems such as 1T-TaS 2 and Bi-2212, pronounced gap features corresponding to the Mott and superconducting gaps were respectively observed at T = 4 K. We observed a gate dependence of the amplitude of the superconducting gap, which has potential applications in a gate-tunable superconducting device with a SiO 2 /Si substrate. For In/10 nm-thick 2H-MoS 2 devices, differential conductance shoulders at bias voltages of approximately ± 0.45 V were observed, which were attributed to the semiconducting gap. These results show that In-contacted vdW gap tunneling spectroscopy in a fashion of field-effect transistor provides feasible and reliable ways to investigate electronic structures of vdW materials., (© 2021. The Author(s).)

The adsorption of acetonitrile (CH 3 CN) on Si(111)-(7 × 7) at a room temperature has been investigated using scanning tunneling microscopy (STM) and first-principles calculations. The site-specific information on adsorption enables us to understand the site-by-site and step-by-step adsorption mechanism. From theoretical simulations, the most stable configuration of CH 3 CN on Si(111)-(7 × 7) is found to be a molecularly chemisorbed CH 3 CN with the carbon and nitrogen atoms of CN bonded to the rest atom and adatom on the Si surface, respectively. Some chemisorption-induced features in the STM topographic image are assigned based on the theoretical calculations., Competing Interests: The authors declare no competing financial interest.

There have been rapidly increasing demands for flexible lighting apparatus, and micrometer-scale light-emitting diodes (LEDs) are regarded as one of the promising lighting sources for deformable device applications. Herein, we demonstrate a method of creating a deformable LED, based on remote heteroepitaxy of GaN microrod (MR) p - n junction arrays on c -Al 2 O 3 wafer across graphene. The use of graphene allows the transfer of MR LED arrays onto a copper plate, and spatially separate MR arrays offer ideal device geometry suitable for deformable LED in various shapes without serious device performance degradation. Moreover, remote heteroepitaxy also allows the wafer to be reused, allowing reproducible production of MR LEDs using a single substrate without noticeable device degradation. The remote heteroepitaxial relation is determined by high-resolution scanning transmission electron microscopy, and the density functional theory simulations clarify how the remote heteroepitaxy is made possible through graphene., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

In optoelectronic devices based on two-dimensional (2D) semiconductor heterojunctions, the efficient charge transport of photogenerated carriers across the interface is a critical factor to determine the device performances. Here, we report an unexplored approach to boost the optoelectronic device performances of the WSe 2 -MoS 2 p - n heterojunctions via the monolithic-oxidation-induced doping and resultant modulation of the interface band alignment. In the proposed device, the atomically thin WO x layer, which is directly formed by layer-by-layer oxidation of WSe 2 , is used as a charge transport layer for promoting hole extraction. The use of the ultrathin oxide layer significantly enhanced the photoresponsivity of the WSe 2 -MoS 2 p - n junction devices, and the power conversion efficiency increased from 0.7 to 5.0%, maintaining the response time. The enhanced characteristics can be understood by the formation of the low Schottky barrier and favorable interface band alignment, as confirmed by band alignment analyses and first-principle calculations. Our work suggests a new route to achieve interface contact engineering in the heterostructures toward realizing high-performance 2D optoelectronics.

Hexagonal boron nitride (hBN) is an insulating two-dimensional (2D) material with a large bandgap. Although known for its interfacing with other 2D materials and structural similarities to graphene, the potential use of hBN in 2D electronics is limited by its insulating nature. Here, we report atomically sharp twin boundaries at AA'/AB stacking boundaries in chemical vapor deposition-synthesized few-layer hBN. We find that the twin boundary is composed of a 6'6' configuration, showing conducting feature with a zero bandgap. Furthermore, the formation mechanism of the atomically sharp twin boundaries is suggested by an analogy with stacking combinations of AA'/AB based on the observations of extended Klein edges at the layer boundaries of AB-stacked hBN. The atomically sharp AA'/AB stacking boundary is promising as an ultimate 1D electron channel embedded in insulating pristine hBN. This study will provide insights into the fabrication of single-hBN electronic devices., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

We have performed density functional theory calculations to study the effects caused by the interfacial structure between 2D-MoS 2 and 3D-GaN. Two different surface terminations of GaN are considered: Ga-terminated (0001) (Ga-GaN) and N-terminated ([Formula: see text]) (N-GaN) configurations. We confirm that Rashba spin splitting occurs in band structure of MoS 2 on GaN. We also find that the surface states of GaN move to the deep position in band structure in the MoS 2 /Ga-GaN case, while the surface states of GaN are hybridized with MoS 2 near the Fermi level for the MoS 2 /N-GaN case. Furthermore, we investigate the variation in electronic structure of MoS 2 /GaN heterostructures depending on the number of MoS 2 layers. Especially, the top layer MoS 2 of the 2L-MoS 2 /GaN structures shows both n-type and p-type properties depending on the GaN surface termination. As a result, we suggest that the electrical characteristics of the 2D/3D heterostructures could be controlled by the surface terminations of substrate materials.

A new compound material of 2D hydrofluorinated graphene (HFG) is demonstrated whose relative hydrogen/fluorine concentrations can be tailored between the extremes of either hydrogenated graphene (HG) and fluorinated graphene (FG). The material is fabricated through subsequent exposures to indirect hydrogen plasma and xenon difluoride (XeF 2 ). Controlling the relative concentration in the HFG compound enables tailoring of material properties between the extremes offered by the constituent materials and in-plane patterning produces micrometer-scale regions with different surface properties. The utility of the technique to tailor the surface wettability, surface friction, and electrical conductivity is demonstrated. HFG compounds display wettability between the extremes of pure FG with contact angle of 95° ± 5° and pure HG with contact angle of 42° ± 2°. Similarly, the HFG surface friction may be tailored between the two extremes. Finally, the HFG electrical conductivity tunes through five orders of magnitude when transitioning from FG to HG. When combined with simulation, the electrical measurements reveal the mechanism producing the compound to be a dynamic process of adatom desorption and replacement. This study opens a new class of 2D compound materials and innovative chemical patterning with applications for atomically thin 2D circuits consisting of chemically/electrically modulated regions., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The valid strong THz absorption at 1.58 THz was probed in the organic-inorganic hybrid perovskite thin film, CH 3 NH 3 PbI 3 , fabricated by sequential vacuum evaporation method. In usual solution-based methods such as 2-step solution and antisolvent, we observed the relatively weak two main absorption peaks at 0.95 and 1.87 THz. The measured absorption spectrum is analyzed by density-functional theory calculations. The modes at 0.95 and 1.87 THz are assigned to the Pb-I vibrations of the inorganic components in the tetragonal phase. By contrast, the origin of the 1.58 THz absorption is due to the structural deformation of Pb-I bonding at the grain boundary incorporated with a CH 3 NH 2 molecular defect.

There have been a few studies of heterojunctions composed of two-dimensional transition-metal dichalcogenides (TMDs) and an oxide layer, but such studies of high-performance electric and optoelectronic devices are essential. Such heterojunctions with low-resistivity metal contacts are needed by the electronics industry to fabricate efficient diodes and photovoltaic devices. Here, a van der Waals heterojunction composed of p-type black phosphorus (p-BP) and n-type indium-gallium-zinc oxide (n-IGZO) films with low-resistivity metal contacts is reported, and it demonstrates high rectification. The low off-state leakage current in the thick IGZO film accounts for the high rectification ratio in a sharp interface of p-BP/n-IGZO devices. For electrostatic gate control, an ionic liquid is introduced to achieve a high rectification ratio of 9.1 × 10 4 . The photovoltaic measurements of p-BP/n-IGZO show fast rise and decay times, significant open-circuit voltage and short-circuit current, and a high photoresponsivity of 418 mA/W with a substantial external quantum efficiency of 12.1%. The electric and optoelectronic characteristics of TMDs/oxide layer van der Waals heterojunctions are attractive for industrial applications in the near future.

Using first-principles calculations, we investigate an atomic impurity at the interface of a van der Waals heterostructure (vdW heterostructure) consisting of a zigzag graphene nanoribbon (ZGNR) and a hexagonal boron nitride (h-BN) sheet. To find effects of atomic intercalation on geometrical and electronic properties of the ZGNR on the h-BN sheet, various types of impurity atoms are considered. The embedded atoms are initially placed at the edge or the middle of the ZGNR located on the h-BN sheet. Our results demonstrate that most of the impurity atoms are more stable at the edge than at the middle in all cases we consider. Especially, a nickel atom has the smallest energy difference (~0.15 eV) between the two embedding positions, which means that the Ni atom is relatively easy to intercalate in the structure. Finally, we discuss magnetic properties for the vdW heterostructure with an intercalated atom.

Two-dimensional atomic layered materials (2d-ALMs) are emerging candidates for use as epitaxial seed substrates for transferrable epilayers. However, the micrometer-sized domains of 2d-ALMs preclude their practical use in epitaxy because they cause crystallographically in-plane disordering of the overlayer. Ultrathin graphene can penetrate the electric dipole momentum from an underlying crystal layer to the graphene surface, which then drives it to crystallize the overlayer during the initial growth stage, thus resulting in substantial energy saving. This study demonstrates the remote homoepitaxy of ZnO microrods (MRs) on ZnO substrates across graphene layers via a hydrothermal method. Despite the presence of poly-domain graphene in between the ZnO substrate and ZnO MRs, the MRs were epitaxially grown on a- and c-plane ZnO substrates, whose in-plane alignments were homogeneous within the wafer's size. Transmission electron microscopy revealed a homoepitaxial relationship between the overlayer MRs and the substrate. Density-functional theory calculations suggested that the charge redistribution occurring near graphene induces the electric dipole formation, so the attracted adatoms led to the formation of the remote homoepitaxial overlayer. Due to a strong potential field caused by long-range charge transfer given from the substrate, even the use of bi-layer and tri-layer graphene resulted in remote homoepitaxial ZnO MRs. The effects of substrate crystal planes were also theoretically and empirically investigated. The ability of graphene, which can be released from the mother substrate without covalent bonds, was utilized to transfer the overlayer MR arrays. This method opens a way for producing well aligned, transferrable epitaxial nano/microstructure arrays while regenerating the substrate for cost-saving device manufacturing.

For utilization of two-dimensional (2D) materials as electronic devices, their mixed-dimensional heterostructures with three-dimensional (3D) materials are receiving much attention. In this study, we have investigated the atomic and electronic structures of the 2D/3D heterojunction between MoS2 and Si(100) using density functional theory calculations; especially, we focus on the contact behavior dependence on the interfacial structures of heterojunctions by considering two types of surface termination of Si(100) surfaces. Calculations show that MoS2 and clean Si(100) form an almost n-type ohmic contact with a very small Schottky barrier height (SBH) due to strong covalent bonds between them, and that the contact between MoS2 and H-covered Si(100) makes a p-n heterojunction with weak van der Waals interactions. Such a difference in contact behaviors can be explained by different electric dipole formation at the heterojunction interfaces. Overall, it is concluded that contact properties can be varied depending on the interfacial structures of 2D(MoS2)/3D(Si) semiconductor heterojunctions.

Black Phosphorus (BP) is an excellent material from the post graphene era due to its layer dependent band gap, high mobility and high I on /I off . However, its poor stability in ambient poses a great challenge for its practical and long-term usage. The optical visualization of the oxidized BP is the key and the foremost step for its successful passivation from the ambience. Here, we have conducted a systematic study of the oxidation of the BP and developed a technique to optically identify the oxidation of the BP using Liquid Crystal (LC). It is interesting to note that we found that the rapid oxidation of the thin layers of the BP makes them disappear and can be envisaged by using the alignment of the LC. The molecular dynamics simulations also proved the preferential alignment of the LC on the oxidized BP. We believe that this simple technique will be effective in passivation efforts of the BP, and will enable it for exploitation of its properties in the field of electronics.

Graphene oxide (GO) modulates the functions of antigen-presenting cells including dendritic cells (DCs). Although carbon nanotubes affect expression of the MHC class I-like CD1d molecule, whether GO can influence immune responses of CD1d-dependent invariant natural killer T (iNKT) cells remains unclear. Here, we investigated the impact of GO on inflammatory responses mediated by α-galactosylceramide (α-GalCer), an iNKT cell agonist. We found that in vivo GO treatment substantially inhibited the capacity of α-GalCer to induce the iNKT cell-mediated trans-activation of and cytokine production by innate and innate-like cells, including DCs, macrophages, NK cells, and γδ T cells. Such effects of GO on α-GalCer-induced inflammatory responses closely correlated with iNKT cell polarization towards TGFβ production, which also explains the capacity of GO to expand regulatory T cells. Interestingly, the absence of TLR4, a receptor for GO, failed to downregulate, and instead partially enhanced the anti-inflammatory activity of GO against α-GalCer-elicited responses, implying negative effects of TLR4 signaling on the anti-inflammatory properties of GO. By employing an α-GalCer-induced sepsis model, we further demonstrated that GO treatment significantly protected mice from α-GalCer-induced lethality. Taken together, we provide strong evidence that GO holds promise as an adjuvant to modulate iNKT cell responses for immunotherapy.

To understand the instability of Sn-based perovskite, CH 3 NH 3 SnI 3 , photoelectron spectroscopy with synchrotron radiation and theoretical calculations, such as density functional theory and ab initio molecular dynamics, were performed. Findings from this experimental and theoretical study highlight the crucial changes of surface-chemical states, the broken chemical bondings in Sn-I, and the depletion of a CH 3 -NH 3 + cation on the surface region. The material instability origin of Sn-based perovskite can be explained by the chemical state instability in the surface.

Heterostructures comprising two-dimensional (2D) semiconductors fabricated by individual stacking exhibit interesting characteristics owing to their 2D nature and atomically sharp interface. As an emerging 2D material, black phosphorus (BP) nanosheets have drawn much attention because of their small band gap semiconductor characteristics along with high mobility. Stacking structures composed of p-type BP and n-type transition metal dichalcogenides can produce an atomically sharp interface with van der Waals interaction which leads to p-n diode functionality. In this study, for the first time, we fabricated a heterojunction p-n diode composed of BP and WS 2 . The rectification effects are examined for monolayer, bilayer, trilayer, and multilayer WS 2 flakes in our BP/WS 2 van der Waals heterojunction diodes and also verified by density function theory calculations. We report superior functionalities as compared to other van der Waals heterojunction, such as efficient gate-dependent static rectification of 2.6 × 10 4 , temperature dependence, thickness dependence of rectification, and ideality factor of the device. The temperature dependence of Zener breakdown voltage and avalanche breakdown voltage were analyzed in the same device. Additionally, superior optoelectronic characteristics such as photoresponsivity of 500 mA/W and external quantum efficiency of 103% are achieved in the BP/WS 2 van der Waals p-n diode, which is unprecedented for BP/transition metal dichalcogenides heterostructures. The BP/WS 2 van der Waals p-n diodes have a profound potential to fabricate rectifiers, solar cells, and photovoltaic diodes in 2D semiconductor electronics and optoelectronics.

P-N junctions represent the fundamental building blocks of most semiconductors for optoelectronic functions. This work demonstrates a technique for forming a WS 2 /Si van der Waals junction based on mechanical exfoliation. Multilayered WS 2 nanoflakes were exfoliated on the surface of bulk p-type Si substrates using a polydimethylsiloxane stamp. We found that the fabricated WS 2 /Si p-n junctions exhibited rectifying characteristics. We studied the effect of annealing processes on the performance of the WS 2 /Si van der Waals p-n junction and demonstrated that annealing improved its electrical characteristics. However, devices with vacuum annealing have an enhanced forward-bias current compared to those annealed in a gaseous environment. We also studied the top-gate-tunable rectification characteristics across the p-n junction interface in experiments as well as density functional theory calculations. Under various temperatures, Zener breakdown occurred at low reverse-bias voltages, and its breakdown voltage exhibited a negative coefficient of temperature. Another breakdown voltage was observed, which increased with temperature, suggesting a positive coefficient of temperature. Therefore, such a breakdown can be assigned to avalanche breakdown. This work demonstrates a promising application of two-dimensional materials placed directly on conventional bulk Si substrates.

Electrochemical intercalation is a powerful method for tuning the electronic properties of layered solids. In this work, we report an electrochemical strategy to controllably intercalate lithium ions into a series of van der Waals (vdW) heterostructures built by sandwiching graphene between hexagonal boron nitride (h-BN). We demonstrate that encapsulating graphene with h-BN eliminates parasitic surface side reactions while simultaneously creating a new heterointerface that permits intercalation between the atomically thin layers. To monitor the electrochemical process, we employ the Hall effect to precisely monitor the intercalation reaction. We also simultaneously probe the spectroscopic and electrical transport properties of the resulting intercalation compounds at different stages of intercalation. We achieve the highest carrier density >5 × 10 13 cm 2 with mobility >10 3 cm 2 /(V s) in the most heavily intercalated samples, where Shubnikov-de Haas quantum oscillations are observed at low temperatures. These results set the stage for further studies that employ intercalation in modifying properties of vdW heterostructures.

The atomic, electronic, and magnetic properties of vacancy structures with triangular shape related to their growth in single hexagonal boron nitride (h-BN) sheet are investigated using density functional theory calculations. We find that the optimized structures of triangular vacancies depend on the vacancy sizes with N-terminated zigzag edge. Then, vacancy structures obtained during the vacancy evolution in h-BN sheet are considered by removing a boron-nitrogen pair (BN pair) from edges of triangular vacancies. The magnetic properties of those vacancy structures are investigated by local density of states and spin densities. It is found that the stability of the optimized structures with a BN missing pair depends on the BN-pair missing position: the most stable structure is a BN-pair missing structure at the edge face region with the smallest magnetic moment.

The special properties of graphene can be largely influenced by point defects in the lattice. However, TEM studies of topological defects in few-layered graphene have rarely been reported. In this work, the two simplest forms of point defects monovacancy and divacancy in twisted bilayer graphene are characterized using aberration-corrected transmission electron microscopy (AC-TEM) at 80 kV. A convenient approach by using a negative mask in the fast Fourier transform (FFT) has been applied to separate the image signal of the two graphene layers. In the study combined with density functional theory (DFT) calculations and tight-binding molecular dynamics simulations, the analysis of the defect structure and movement shows the stability and migration behavior of both defects. DFT calculations indicate that the migration of monovacancy in bilayer graphene needs to overcome a higher energy barrier.

This corrects the article DOI: 10.1038/srep21788.

We have performed density functional theory (DFT) calculations of the atomic and electronic structures of ethylenediamine on Ge(100). The two amine groups in ethylenediamine can interact with germanium surface atoms through a N-H dissociative nucleophilic reaction and/or N-dative bonding with an electron-deficient down Ge atom. Of the monodentate and row-bridged bidentate structures that formed, the dative-bonded configurations were found to be more stable than the NH dissociative adsorption structures. The formation of row-bridged bidentate, structures is more favorable than that of on-top or end-bridged structures. In simulated STM images, the three types of row-bridged adsorption structure have characteristic features, and the row-bridged dative-bonded configuration gives rise to features due to both adsorbed ethylenediamine molecules and the underlying Ge atoms.

Using density functional theory calculations, we have studied the edge-functionalization of armchair graphene nanoribbons (AGNRs) with pentagonal-hexagonal edge structures. While the AGNRs with pentagonal-hexagonal edge structures (labeled (5,6)-AGNRs) are metallic, the edge-functionalized (5,6)-AGNRs with substitutional atoms opens a band gap. We find that the band structures of edge-functionalized (5,6)-N-AGNRs by substitution resemble those of defect-free (N-1)-AGNR at the Γ point, whereas those at the X point show the original ones of the defect-free N-AGNR. The overall electronic structures of edge-functionalized (5,6)-AGNRs depend on the number of electrons, supplied by substitutional atoms, at the edges of functionalized (5,6)-AGNRs.

Metal-doped graphene produces magnetic moments that have potential application in spintronics. Here we use density function theory computational methods to show how the magnetic interaction between metal atoms doped in graphene can be controlled by the degree of flexure in a graphene membrane. Bending graphene by flexing causes the distance between two substitutional Fe atoms covalently bonded in graphene to gradually increase and these results in the magnetic moment disappearing at a critical strain value. At the critical strain, a carbon atom can enter between the two Fe atoms and blocks the interaction between relevant orbitals of Fe atoms to quench the magnetic moment. The control of interactions between doped atoms by exploiting the mechanical flexibility of graphene is a unique approach to manipulating the magnetic properties and opens up new opportunities for mechanical-magnetic 2D device systems.

An in situ heating holder inside an aberration-corrected transmission electron microscope (AC-TEM) is used to investigate the real-time atomic level dynamics associated with heterogeneous nucleation and growth of graphene from Au nanoparticle seeds. Heating monolayer graphene to an elevated temperature of 800 °C removes the majority of amorphous carbon adsorbates and leaves a clean surface. The aggregation of Au impurity atoms into nanoparticle clusters that are bound to the surface of monolayer graphene causes nucleation of secondary graphene layers from carbon feedstock present within the microscope chamber. This enables the in situ study of heterogeneous nucleation and growth of graphene at the atomic level. We show that the growth mechanism consists of alternating C cluster attachment and indentation filling to maintain a uniform growth front of lowest energy. Back-folding of the graphene growth front is observed, followed by a process that involves flipping back and attaching to the surrounding region. We show how the highly polycrystalline graphene seed evolves with time into a higher order crystalline structure using a combination of AC-TEM and tight-binding molecular dynamics (TBMD) simulations. This helps understand the detailed lowest-energy step-by-step pathways associated with grain boundaries (GB) migration and crystallization processes. We find the motion of the GB is discontinuous and mediated by both bond rotation and atom evaporation, supported by density functional theory calculations and TBMD. These results provide insights into the formation of crystalline seed domains that are generated during bottom-up graphene synthesis.

Metal-insulator transitions in low-dimensional materials under ambient conditions are rare and worth pursuing due to their intriguing physics and rich device applications. Monolayer MoTe2 and WTe2 are distinguished from other TMDs by the existence of an exceptional semimetallic distorted octahedral structure (T') with a quite small energy difference from the semiconducting H phase. In the process of transition metal alloying, an equal stability point of the H and the T' phase is observed in the formation energy diagram of monolayer WxMo1-xTe2. This thermodynamically driven phase transition enables a controlled synthesis of the desired phase (H or T') of monolayer WxMo1-xTe2 using a growth method such as chemical vapor deposition (CVD) and molecular beam epitaxy (MBE). Furthermore, charge mediation, as a more feasible method, is found to make the T' phase more stable than the H phase and induce a phase transition from the H phase (semiconducting) to the T' phase (semimetallic) in monolayer WxMo1-xTe2 alloy. This suggests that a dynamic metal-insulator phase transition can be induced, which can be exploited for rich phase transition applications in two-dimensional nanoelectronics.

Securing a semiconducting bandgap is essential for applying graphene layers in switching devices. Theoretical studies have suggested a created bulk bandgap in a graphene layer by introducing an asymmetry between the A and B sub-lattice sites. A recent transport measurement demonstrated the presence of a bandgap in a graphene layer where the asymmetry was introduced by placing a graphene layer on a hexagonal boron nitride (h-BN) substrate. Similar bandgap has been observed in graphene layers on metal substrates by local probe measurements; however, this phenomenon has not been observed in graphene layers on a near-insulating substrate. Here, we present bulk bandgap-like features in a graphene layer epitaxially grown on an h-BN substrate using scanning tunneling spectroscopy. We observed edge states at zigzag edges, edge resonances at armchair edges, and bandgap-like features in the bulk.

In this Letter, we use first-principles simulations to demonstrate the absence of Fermi-level pinning when graphene is in contact with transition metal dichalcogenides (TMDs). We find that formation of either an ohmic or Schottky contact is possible. Then we show that, due to the shallow density of states around its Fermi level, the work function of graphene can be tuned by ion adsorption. Finally we combine work function tuning of graphene and an ideal contact between graphene and TMDs to propose an ionic barristor design that can tune the work function of graphene with a much wider margin than current barristor designs, achieving a dynamic switching among p-type ohmic contact, Schottky contact, and n-type ohmic contact in one device.

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10(-3) bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc- or V-porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials.

Bilayer graphene (BLG) with a tunable band gap appears interesting as an alternative to graphene for practical applications; thus, its transport properties are being actively pursued. Using density functional theory and perturbation analysis, we investigated, under an external electric field, the electronic properties of BLG in various stackings relevant to recently observed complex structures. We established the first phase diagram summarizing the stacking-dependent gap openings of BLG for a given field. We further identified high-density midgap states, localized on grain boundaries, even under a strong field, which can considerably reduce the overall transport gap.

Carbon nanotubes (CNTs) have shown great potential in biomedical fields. However, in vivo applications of CNTs for regenerative medicine have been hampered by difficulties associated with the fabrication of three-dimensional (3D) scaffolds of CNTs due to CNTs' nano-scale nature. In this study, we devised a new method for biosynthesis of CNT-based 3D scaffold by in situ hybridizing CNTs with bacterial cellulose (BC), which has a structure ideal for tissue-engineering scaffolds. This was achieved simply by culturing Gluconacetobacter xylinus, BC-synthesizing bacteria, in medium containing CNTs. However, pristine CNTs aggregated in medium, which hampers homogeneous hybridization of CNTs with BC scaffolds, and the binding energy between hydrophobic pristine CNTs and hydrophilic BC was too small for the hybridization to occur. To overcome these problems, an amphiphilic comb-like polymer (APCLP) was adsorbed on CNTs. Unlike CNT-coated BC scaffolds (CNT-BC-Imm) formed by immersing 3D BC scaffolds in CNT solution, the APCLP-adsorbed CNT-BC hybrid scaffold (CNT-BC-Syn) showed homogeneously distributed CNTs throughout the 3D microporous structure of BC. Importantly, in contrast to CNT-BC-Imm scaffolds, CNT-BC-Syn scaffolds showed excellent osteoconductivity and osteoinductivity that led to high bone regeneration efficacy. This strategy may open a new avenue for development of 3D biofunctional scaffolds for regenerative medicine., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The production of holes by electron beam irradiation in hexagonal boron nitride (hBN), which has a lattice similar to that of graphene, is monitored over time using atomic resolution transmission electron microscopy. The holes appear to be initiated by the formation of a vacancy of boron and grow in a manner that retains an overall triangular shape. The hole growth process involves the formation of single chains of B and N atoms and is accompanied by the ejection of atoms and bundles of atoms along the hole edges, as well as atom migration. These observations are compared to density functional theory calculations and molecular dynamics simulations.

We investigate the electronic properties of bilayer MoS2 exposed to an external electric field by using first-principles calculations. It is found that a larger interlayer distance, referring to that by standard density functional theory (DFT) with respect to that by DFT with empirical dispersion corrections, makes indirect-direct band gap transition possible by electric control. We show that external electric field effectively manipulates the valence band contrast between the K- and Γ-valleys by forming built-in electric dipole fields, which realizes an indirect-direct transition before a semiconductor-metal transition happens. Our results provide a novel efficient access to tune the electronic properties of two-dimensional layered materials.

We report on the syntheses of core-shell Fex@Pt (x=0.4-1.2) nanoparticles (NPs) with Pt-shell thickness systematically controlled while the overall particle size is constant. The syntheses were achieved via one-pot ultrasound-assisted polyol synthesis (UPS) reactions. Fe1.2@Pt showed a record-breaking high core-element content (55 at%) of core-shell NPs. Based on observations from a series of control experiments, we propose a mechanism of the NPs' formation that enables control of shell thickness in UPS reactions. Fex@Pt NPs showed drastic enhancements in mass and specific activity for oxygen reduction reaction (ORR) and significantly enhanced durability compared to commercial Pt NPs. Fex@Pt with a 1 (monolayer) ML Pt shell showed the highest activity. The ab initio density functional theory calculations on the binding energies of oxygen species on the surfaces of Fex@Pt NPs showed that the 1 ML case is most favourable for the ORR, and in good agreement with the experimental results.

A periodically modulated graphene (PMG) generated by nanopatterned surfaces is reported to profoundly modify the intrinsic electronic properties of graphene. The temperature dependence of the sheet resistivity and gate response measurements clearly show a semiconductor-like behavior. Raman spectroscopy reveals significant shifts of the G and the 2D modes induced by the interaction with the underlying grid-like nanostructure. The influence of the periodic, alternating contact with the substrate surface was studied in terms of strain caused by bending of graphene and doping through chemical interactions with underlying substrate atoms. Electronic structure calculations performed on a model of PMG reveals that it is possible to tune a band gap within 0.14-0.19 eV by considering both the periodic mechanical bending and the surface coordination chemistry. Therefore, the PMG can be regarded as a further step toward band gap engineering of graphene devices.

Using spin-polarized density functional theory calculations, we study binding properties of small metal nanoclusters (Cu(13) and Al(13)) onto carbon nanotubes (CNTs). On defect-free CNTs, the binding affinity with the Cu or Al cluster is very weak. When various defects such as vacancies, substitutional nickel defects, and nickel adatoms are introduced in CNTs to increase the binding strength, the binding energies of the metal nanoclusters increase substantially irrespective of types of defects. The effect of the Ni adatom is especially noticeable. Our results propose a method for improving the wettability of metal-CNT complex composites.

Using density functional theory calculations, we have investigated the interactions between hydrogen molecules and metalloporphyrins. A metal atom, such as Ca or Ti, is introduced for incorporation in the central N(4) cavity. Within local density approximation (generalized gradient approximation), we find that the average binding energy of H(2) to the Ca atom is about 0.25 (0.1) eV/H(2) up to four H(2) molecules, whereas that to the Ti atom is about 0.6 (0.3) eV per H(2) up to two H(2) molecules. Our analysis of orbital hybridization between the inserted metal atom and molecular hydrogen shows that H(2) binds weakly to Ca-porphyrin through a weak electric polarization in dihydrogen, but is strongly hybridized with Ti-porphyrin through the Kubas interaction. The presence of d orbitals in Ti may explain the difference in the interaction types., (© 2011 American Institute of Physics)

We performed first-principles calculations to investigate the hydrogen storage characteristics of carbon-based 3-D solid structures, called covalently bonded graphenes (CBGs). Using the density functional method and the Møller-Plesset perturbation method, we show that H2 molecular binding in the CBGs is stronger than that on an isolated graphene with an increase of 20 to approximately 150% in binding energy, which is very promising for storage at ambient conditions. We also suggest that the CBGs of appropriate size can effectively work as frameworks for transition metal dispersion. The adsorption properties of hydrogen on the metal atoms dispersed inside the CBGs are also presented.

The adsorption structures of pyrrole (C(4)H(5)N) on a Ge(100) surface at various coverages have been investigated with both scanning tunneling microscopy (STM) and ab initio density-functional theory (DFT) calculations. Three distinct features are observed in the STM images at low coverages. The comparison of the STM images with the simulation reveals that the most dominant flowerlike feature with a dark side is that the adsorbed pyrrole molecules with H dissociated form bridges between two down Ge atoms of neighboring Ge dimer rows through N-Ge bonding and beta-carbon-Ge interaction. The flowerlike feature without a dark side is also observed as a minority, which is identified as nearly the same structure as the most dominant one where a dissociated H is out of the feature. The third feature showing bright protrusions may be due to a C- and N-end-on (CN) configuration, where the pyrrole molecule is located on one dimer row. At higher coverages, the number of localized configurations increases.

The adsorption and decomposition of water on Ge(100) have been investigated using real-time scanning tunneling microscopy (STM) and density-functional theory (DFT) calculations. The STM results revealed two distinct adsorption features of H2O on Ge(100) corresponding to molecular adsorption and H-OH dissociative adsorption. In the molecular adsorption geometry, H2O molecules are bound to the surface via Ge-O dative bonds between the O atom of H2O and the electrophilic down atom of the Ge dimer. In the dissociative adsorption geometry, the H2O molecule dissociates into H and OH, which bind covalently to a Ge-Ge dimer on Ge(100) in an H-Ge-Ge-OH configuration. The DFT calculations showed that the dissociative adsorption geometry is more stable than the molecular adsorption geometry. This finding is consistent with the STM results, which showed that the dissociative product becomes dominant as the H2O coverage is increased. The simulated STM images agreed very well with the experimental images. In the real-time STM experiments, we also observed a structural transformation of the H2O molecule from the molecular adsorption to the dissociative adsorption geometry.

The adsorption of pyrimidine onto Ge(100) surfaces has been investigated using real-time scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density-functional theory (DFT) calculations. Our results show that the adsorbed pyrimidine molecules are tilted about 40 degrees with respect to the Ge surface, and through a Lewis acid-base reaction form bridges between the down-Ge atoms of neighboring Ge dimer rows by double Ge-N dative bonding without loss of aromaticity. For coverages of pyrimidine up to 0.25 ML, a well-ordered c(4x2) structure results from states that appear in STM micrographs as oval-shaped protrusions, which correspond to pyrimidine molecules datively adsorbed on every other dimer. However, above 0.25 ML, the oval-shaped protrusions gradually change into brighter zigzag lines. At 0.50 ML, a p(2x2) structure results from the states that appear in STM as zigzag lines. The zigzag lines are formed by the attachment of pyrimidine molecules to the down-Ge atoms of every Ge dimer. However, the unstable p(2x2) structure eventually reconstructs into a c(4x2) structure due to steric hindrance between the adsorbed pyrimidine molecules after stopping the exposure of pyrimidine to the surface.