We introduce the 2D counterpart of layered black phosphorus, which we call phosphorene, as an unexplored p-type semiconducting material. Same as graphene and MoS2, single-layer phosphorene is flexible and can be mechanically exfoliated. We find phosphorene to be stable and, unlike graphene, to have an inherent, direct, and appreciable band gap. Our ab initio calculations indicate that the band gap is direct, depends on the number of layers and the in-layer strain, and is significantly larger than the bulk value of 0.31-0.36 eV. The observed photoluminescence peak of single-layer phosphorene in the visible optical range confirms that the band gap is larger than that of the bulk system. Our transport studies indicate a hole mobility that reflects the structural anisotropy of phosphorene and complements n-type MoS2. At room temperature, our few-layer phosphorene field-effect transistors with 1.0 μm channel length display a high on-current of 194 mA/mm, a high hole field-effect mobility of 286 cm(2)/V·s, and an on/off ratio of up to 10(4). We demonstrate the possibility of phosphorene integration by constructing a 2D CMOS inverter consisting of phosphorene PMOS and MoS2 NMOS transistors.
We investigate a previously unknown phase of phosphorus that shares its layered structure and high stability with the black phosphorus allotrope. We find the in-plane hexagonal structure and bulk layer stacking of this structure, which we call "blue phosphorus," to be related to graphite. Unlike graphite and black phosphorus, blue phosphorus displays a wide fundamental band gap. Still, it should exfoliate easily to form quasi-two-dimensional structures suitable for electronic applications. We study a likely transformation pathway from black to blue phosphorus and discuss possible ways to synthesize the new structure.
Based on ab initio density functional calculations, we propose γ-P and δ-P as two additional stable structural phases of layered phosphorus besides the layered α-P (black) and β-P (blue) phosphorus allotropes. Monolayers of some of these allotropes have a wide band gap, whereas others, including γ-P, show a metal-insulator transition caused by in-layer strain or changing the number of layers. An unforeseen benefit is the possibility to connect different structural phases at no energy cost. This becomes particularly valuable in assembling heterostructures with well-defined metallic and semiconducting regions in one contiguous layer.
We demonstrate an aerosol CVD process to dry deposit large-area SWCNT networks with tunable conductivity and optical transmittance on a wide range of substrates including flexible polymers. These SWCNT networks can be chemically doped to reach a sheet resistance of as low as 110 Ω/⟨ at 90% optical transmittance. A wide application potential of these networks is demonstrated by fabricating SWCNT network-based devices such as a transparent capacitive touch sensors, thin-film transistors (TFTs), and bright organic light-emitting diodes (OLEDs).
Phosphorene, an emerging two-dimensional material, has received considerable attention due to its layer-controlled direct bandgap, high carrier mobility, negative Poisson's ratio and unique in-plane anisotropy. As cousins of phosphorene, 2D group-VA arsenene, antimonene and bismuthene have also garnered tremendous interest due to their intriguing structures and fascinating electronic properties. 2D group-VA family members are opening up brand-new opportunities for their multifunctional applications encompassing electronics, optoelectronics, topological spintronics, thermoelectrics, sensors, Li- or Na-batteries. In this review, we extensively explore the latest theoretical and experimental progress made in the fundamental properties, fabrications and applications of 2D group-VA materials, and offer perspectives and challenges for the future of this emerging field.
Sensitive dependence of the electronic structure on the number of layers in few-layer phosphorene raises a question about the true nature of the interlayer interaction in so-called "van der Waals (vdW) solids". We performed quantum Monte Carlo calculations and found that the interlayer interaction in bulk black phosphorus and related few-layer phosphorene is associated with a significant charge redistribution that is incompatible with purely dispersive forces and not captured by density functional theory calculations with different vdW corrected functionals. These findings confirm the necessity of more sophisticated treatment of nonlocal electron correlation in total energy calculations.
Despite extensive research for more than 200 years, the experimental isolation of monatomic sulphur chains, which are believed to exhibit a conducting character, has eluded scientists. Here we report the synthesis of a previously unobserved composite material of elemental sulphur, consisting of monatomic chains stabilized in the constraining volume of a carbon nanotube. This one-dimensional phase is confirmed by high-resolution transmission electron microscopy and synchrotron X-ray diffraction. Interestingly, these one-dimensional sulphur chains exhibit long domain sizes of up to 160 nm and high thermal stability (~800 K). Synchrotron X-ray diffraction shows a sharp structural transition of the one-dimensional sulphur occurring at ~450–650 K. Our observations, and corresponding electronic structure and quantum transport calculations, indicate the conducting character of the one-dimensional sulphur chains under ambient pressure. This is in stark contrast to bulk sulphur that needs ultrahigh pressures exceeding ~90 GPa to become metallic.
We have developed a magnesia (MgO)-supported iron-copper (FeCu) catalyst to accomplish the growth of single-walled carbon nanotubes (SWNTs) using carbon monoxide (CO) as the carbon source at ambient pressure. The FeCu catalyst system facilitates the growth of small-diameter SWNTs with a narrow diameter distribution. UV-vis-NIR optical absorption spectra and photoluminescence excitation (PLE) mapping were used to evaluate the relative quantities of the different (n,m) species. We have also demonstrated that the addition of Cu to the Fe catalyst can also cause a remarkable increase in the yield of SWNTs. Finally, a growth mechanism for the FeCu-catalyzed synthesis of SWNTs has been proposed.
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