RESUMEN
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 (â¼106 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.
RESUMEN
The family of group IV-VI monochalcogenides has an atomically puckered layered structure, and their atomic bond configuration suggests the possibility for the realization of various polymorphs. Here, we report the synthesis of the first hexagonal polymorph from the family of group IV-VI monochalcogenides, which is conventionally orthorhombic. Recently predicted four-atomic-thick hexagonal GeSe, so-called γ-GeSe, is synthesized and clearly identified by complementary structural characterizations, including elemental analysis, electron diffraction, high-resolution transmission electron microscopy imaging, and polarized Raman spectroscopy. The electrical and optical measurements indicate that synthesized γ-GeSe exhibits high electrical conductivity of 3 × 105 S/m, which is comparable to those of other two-dimensional layered semimetallic crystals. Moreover, γ-GeSe can be directly grown on h-BN substrates, demonstrating a bottom-up approach for constructing vertical van der Waals heterostructures incorporating γ-GeSe. The newly identified crystal symmetry of γ-GeSe warrants further studies on various physical properties of γ-GeSe.
RESUMEN
The atomic or molecular assembly on 2D materials through the relatively weak van der Waals interaction is quite different from the conventional heteroepitaxy and may result in unique growth behaviors. Here, it is shown that straight 1D cyanide chains display universal epitaxy on hexagonal 2D materials. A universal oriented assembly of cyanide crystals (AgCN, AuCN, and Cu0.5Au0.5CN) is observed, where the chains are aligned along the three zigzag lattice directions of various 2D hexagonal crystals (graphene, h-BN, WS2, MoS2, WSe2, MoSe2, and MoTe2). The potential energy landscape of the hexagonal lattice induces this preferred alignment of 1D chains along the zigzag lattice directions, regardless of the lattice parameter and surface elements as demonstrated by first-principles calculations and parameterized surface potential calculations. Furthermore, the oriented microwires can serve as crystal orientation markers, and stacking-angle-controlled vertical 2D heterostructures are successfully fabricated by using them as markers. The oriented van der Waals epitaxy can be generalized to any hexagonal 2D crystals and will serve as a unique growth process to form crystals with orientations along the zigzag directions by epitaxy.
RESUMEN
A macroscopic film (2.5 cm × 2.5 cm) made by layer-by-layer assembly of 100 single-layer polycrystalline graphene films is reported. The graphene layers are transferred and stacked one by one using a wet process that leads to layer defects and interstitial contamination. Heat-treatment of the sample up to 2800 °C results in the removal of interstitial contaminants and the healing of graphene layer defects. The resulting stacked graphene sample is a freestanding film with near-perfect in-plane crystallinity but a mixed stacking order through the thickness, which separates it from all existing carbon materials. Macroscale tensile tests yields maximum values of 62 GPa for the Young's modulus and 0.70 GPa for the fracture strength, significantly higher than has been reported for any other macroscale carbon films; microscale tensile tests yield maximum values of 290 GPa for the Young's modulus and 5.8 GPa for the fracture strength. The measured in-plane thermal conductivity is exceptionally high, 2292 ± 159 W m-1 K-1 while in-plane electrical conductivity is 2.2 × 105 S m-1 . The high performance of these films is attributed to the combination of the high in-plane crystalline order and unique stacking configuration through the thickness.
RESUMEN
The van der Waals epitaxy of functional materials provides an interesting and efficient way to manipulate the electrical properties of various hybrid two-dimensional (2D) systems. Here we show the controlled epitaxial assembly of semiconducting one-dimensional (1D) atomic chains, AuCN, on graphene and investigate the electrical properties of 1D/2D van der Waals heterostructures. AuCN nanowire assembly is tuned by different growth conditions, although the epitaxial alignment between AuCN chains and graphene remains unchanged. The switching of the preferred nanowire growth axis indicates that diffusion kinetics affects the nanowire formation process. Semiconducting AuCN chains endow the 1D/2D hybrid system with a strong responsivity to photons with an energy above 2.7 eV, which is consistent with the bandgap of AuCN. A large UV response (responsivity â¼104 A/W) was observed under illumination using 3.1 eV (400 nm) photons. Our study clearly demonstrates that 1D chain-structured semiconductors can play a crucial role as a component in multifunctional van der Waals heterostructures.
