Electrical Transport Properties Driven by Unique Bonding Configuration in γ-GeSe.

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 (∼106 S/m) and a relatively low Seebeck coefficient (9.4 µV/K at room temperature) owing to its high p-doping level (5 × 1021 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.

Controlled Bipolar Doping of One-Dimensional van der Waals Nb2Pd3Se8.

Tailoring the electrical properties of one-dimensional (1D) van der Waals (vdW) materials is desirable for their applications toward electronic devices by exploiting their unique characteristics. However, 1D vdW materials have not been extensively investigated for modulation of their electrical properties. Here we control doping levels and types of 1D vdW Nb2Pd3Se8 over a wide energy range by immersion in AuCl3 or ß-nicotinamide adenine dinucleotide (NADH) solutions, respectively. Through spectroscopic analyses and electrical characterizations, we confirm that the charges were effectively transferred to Nb2Pd3Se8, and the dopant concentration was adjusted to the immersion time. Furthermore, we make the axial p-n junction of 1D Nb2Pd3Se8 by a selective area p-doping using the AuCl3 solution, which exhibits rectifying behavior with an Iforward/Ireverse of 81 and an ideality factor of 1.2. Our findings could pave the way to more practical and functional electronic devices based on 1D vdW materials.

Carrier mobility of one-dimensional vanadium selenide (V2Se9) monolayer and nanoribbon systems: DFT study.

Vanadium selenide (V2Se9) is a true one-dimensional (1D) crystal composed of atomic nanochains bonded by van der Waals (vdW) interactions. Recent experiments revealed the mechanical exfoliation of newly synthesized V2Se9. In this study, we predicted the electronic and transport properties of V2Se9through computational analyses. We calculated the intrinsic carrier mobility of V2Se9monolayers (MLs) and nanoribbons (NRs) using density functional theory and deformation potential theory. We found that the electron mobility of the two-dimensional (2D) (010)-plane ML of V2Se9is highly anisotropic, reachingµ2D,ze=1327cm2V-1s-1across the chain direction. The electron mobility of 1D NR systems in a (010)-plane ML of V2Se9along the chain direction continuously increased as the thickness increased from 1-chain to 4-chain NR (width below 3 nm). Interestingly, the electron mobility of 1D 4-chain NR along the chain direction (µ1D,xe=775cm2V-1s-1) was higher than that of a 2D (010)-plane ML (µ2D,xe=567cm2V-1s-1). These results demonstrate the potential of vdW-1D crystal V2Se9as a new nanomaterial for ultranarrow (sub-3 nm width) optoelectronic devices with high electron mobility.

Ta2 Ni3 Se8 : 1D van der Waals Material with Ambipolar Behavior.

In this study, high-purity and centimeter-scale bulk Ta2 Ni3 Se8 crystals are obtained by controlling the growth temperature and stoichiometric ratio between tantalum, nickel, and selenium. It is demonstrated that the bulk Ta2 Ni3 Se8 crystals could be effectively exfoliated into a few chain-scale nanowires through simple mechanical exfoliation and liquid-phase exfoliation. Also, the calculation of electronic band structures confirms that Ta2 Ni3 Se8 is a semiconducting material with a small bandgap. A field-effect transistor is successfully fabricated on the mechanically exfoliated Ta2 Ni3 Se8 nanowires. Transport measurements at room temperature reveal that Ta2 Ni3 Se8 nanowires exhibit ambipolar semiconducting behavior with maximum mobilities of 20.3 and 3.52 cm2 V-1 s-1 for electrons and holes, respectively. The temperature-dependent transport measurement (from 90 to 295 K) confirms the carrier transport mechanism of Ta2 Ni3 Se8 nanowires. Based on these characteristics, the obtained 1D vdW material is expected to be a potential candidate for additional 1D materials as channel materials.

Tuning the electronic properties of highly anisotropic 2D dangling-bond-free sheets from 1D V2Se9 chain structures.

True one-dimensional (1D) van der Waals materials can form two-dimensional (2D) dangling-bond-free anisotropic surfaces. Dangling bonds on surfaces act as defects for transporting charge carriers. In this study, we consider true 1D materials to be V2Se9 chains, and then the electronic structures of 2D sheets composed of true 1D V2Se9 chains are calculated. The (010) plane has indirect bandgap with 0.757 eV (1.768 eV), while the (111̅) plane shows a nearly direct bandgap of 1.047 eV (2.118 eV) for DFT-D3 (HSE06) correction, respectively. The (111̅) plane of V2Se9 is expected to be used in optoelectronic devices because it contains a nearly direct bandgap. Partial charge analysis indicates that the (010) plane exhibits interchain interaction is stronger than the (111̅) plane. To investigate the strain effect, we increased the interchain distance of planes until an indirect-to-direct bandgap transition occurred. The (010) plane then demonstrated a direct bandgap when interchain distance increased by 30%, while the (111̅) plane demonstrated a direct bandgap when the interchain distance increased by 10%. In mechanical sensors, this change in the bandgap was induced by the interchain distance.

Investigation of atomic and electronic properties of 2D-MoS2/3D-GaN mixed-dimensional heterostructures.

We have performed density functional theory calculations to study the effects caused by the interfacial structure between 2D-MoS2 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 MoS2 on GaN. We also find that the surface states of GaN move to the deep position in band structure in the MoS2/Ga-GaN case, while the surface states of GaN are hybridized with MoS2 near the Fermi level for the MoS2/N-GaN case. Furthermore, we investigate the variation in electronic structure of MoS2/GaN heterostructures depending on the number of MoS2 layers. Especially, the top layer MoS2 of the 2L-MoS2/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.

Indirect-direct band gap transition through electric tuning in bilayer MoS2.

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.

Tailored Synthesis of Heterogenous 2D TMDs and Their Spectroscopic Characterization.

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 (WO3 and MoO3) thin films and a diluted H2S precursor, individual MoS2, WS2 films and various MoS2/WS2 hybrid films (Type I: MoxW1-xS2 alloy; Type II: MoS2/WS2 vdWH; Type III: MoS2 dots/WS2). Structural analyses, including optical microscopy, Raman spectroscopy, transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy, and cross-sectional imaging revealed that the A1g and E2g modes of WS2 and MoS2 were sensitive to structural variations, enabling hybrid structure differentiation. Type II showed minimal changes in the MoS2's A1g mode, while Types I and III exhibited a ~2.8 cm-1 blue shift. Furthermore, the A1g mode of WS2 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 MoS2-WS2 interfaces. Our study provides insights into the structural features of diverse hybrid TMD materials, facilitating their differentiation through Raman spectroscopy.

High-throughput manufacturing of epitaxial membranes from a single wafer by 2D materials-based layer transfer process.

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.

Enhanced binding strength between metal nanoclusters and carbon nanotubes with an atomic nickel defect.

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.

Unveiling two-dimensional magnesium hydride as a hydrogen storage material via a generative adversarial network.

This study used an artificial intelligence (AI)-based crystal inverse-design approach to investigate the new phase of two-dimensional (2D) pristine magnesium hydride (Mg x H y ) sheets and verify their availability as a hydrogen storage medium. A 2D binary phase diagram for the generated crystal images was constructed, which was used to identify significant 2D crystal structures. Then, the electronic and dynamic properties of the Mg x H y sheets in low-energy periodic phases were identified via density functional theory (DFT) calculations; this revealed a previously unknown phase of 2D MgH2 with a P4̄m2 space group. In the proposed structure, the adsorption behaviors of the Li-decorated system were investigated for multiple hydrogen molecules. It was confirmed that Li-decorated MgH2 has an expected theoretical gravimetric density of 6 wt%, with an average H2 adsorption energy of -0.105 eV. Therefore, it is anticipated that P4̄m2 MgH2 sheets can be employed effectively as a medium for hydrogen storage. Additionally, this finding indicates that a deep learning-based approach is beneficial for exploring unrevealed 2D materials.

Theoretical Study of Anisotropic Carrier Mobility for Two-Dimensional Nb2Se9 Material.

Finding new materials with satisfying all the desired criteria for nanodevices is an extremely difficult work. Here, we introduce a novel Nb2Se9 material as a promising candidate, capable of overcoming some physical limitations, such as a suitable band gap, high carrier mobility, and chemical stability. Unlike graphene, it has a noticeable band gap and no dangling bonds at surfaces that deteriorate transport properties, owing to its molecular chain structure. Using density functional theory (DFT) calculations with deformation potential (DP) theory, we find that the electron mobility of 2D Nb2Se9 across the axis direction reaches up to 2.56 × 103 cm2 V-1 s-1 and is approximately 2.5-6 times higher than the mobility of other 2D materials, such as MoS2, black phosphorous, and InSe, at room temperature. Moreover, the mobility of 2D Nb2Se9 is highly anisotropic (µ a /µ c ≈ 6.5). We demonstrate the potential of 2D Nb2Se9 for applications in nanoscale electronic devices and, possibly, mid-infrared photodetectors.

One-dimensional van der Waals stacked p-type crystal Ta2Pt3Se8 for nanoscale electronics.

Recently, ternary transition metal chalcogenides Ta2X3Se8 (X = Pd or Pt) have attracted great interest as a class of emerging one-dimensional (1D) van der Waals (vdW) materials. In particular, Ta2Pd3Se8 has been actively studied owing to its excellent charge transport properties as an n-type semiconductor and ultralong ballistic phonon transport properties. Compared to subsequent studies on the Pd-containing material, Ta2Pt3Se8, another member of this class of materials has been considerably less explored despite its promising electrical properties as a p-type semiconductor. Herein, we demonstrate the electrical properties of Ta2Pt3Se8 as a promising channel material for nanoelectronic applications. High-quality bulk Ta2Pt3Se8 single crystals were successfully synthesized by a one-step vapor transport reaction. Scanning Kelvin probe microscopy measurements were used to investigate the surface potential difference and work function of the Ta2Pt3Se8 nanoribbons of various thicknesses. Field-effect transistors fabricated on exfoliated Ta2Pt3Se8 nanoribbons exhibited moderate p-type transport properties with a maximum hole mobility of 5 cm2 V-1 s-1 and an Ion/Ioff ratio of >104. Furthermore, the charge transport mechanism of Ta2Pt3Se8 was analyzed by temperature-dependent transport measurements in the temperature range from 90 to 320 K. To include Ta2Pt3Se8 in a building block for modern 1D electronics, we demonstrate p-n junction characteristics using the electron beam doping method.

Effects of intercalated atoms on electronic structure of graphene nanoribbon/hexagonal boron nitride stacked layer.

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.

Tailoring Surface Properties via Functionalized Hydrofluorinated Graphene Compounds.

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 (XeF2 ). 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.

Energy Bandgap and Edge States in an Epitaxially Grown Graphene/h-BN Heterostructure.

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 situ hybridization of carbon nanotubes with bacterial cellulose for three-dimensional hybrid bioscaffolds.

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.