Two-dimensional (2D) transition-metal dichalcogenides (2D TMDs) in the form of MX2 (M: transition metal, X: chalcogen) exhibit intrinsically anisotropic layered crystallinity wherein their material properties are determined by constituting M and X elements. 2D platinum diselenide (2D PtSe2) is a relatively unexplored class of 2D TMDs with noble-metal Pt as M, offering distinct advantages over conventional 2D TMDs such as higher carrier mobility and lower growth temperatures. Despite the projected promise, much of its fundamental structural and electrical properties and their interrelation have not been clarified, and so its full technological potential remains mostly unexplored. In this work, we investigate the structural evolution of large-area chemical vapor deposition (CVD)-grown 2D PtSe2 layers of tailored morphology and clarify its influence on resulting electrical properties. Specifically, we unveil the coupled transition of structural–electrical properties in 2D PtSe2 layers grown at a low temperature (i.e., 400 °C). The layer orientation of 2D PtSe2 grown by the CVD selenization of seed Pt films exhibits horizontal-to-vertical transition with increasing Pt thickness. While vertically aligned 2D PtSe2 layers present metallic transports, field-effect-transistor gate responses were observed with thin horizontally aligned 2D PtSe2 layers prepared with Pt of small thickness. Density functional theory calculation identifies the electronic structures of 2D PtSe2 layers undergoing the transition of horizontal-to-vertical layer orientation, further confirming the presence of this uniquely coupled structural-electrical transition. The advantage of low-temperature growth was further demonstrated by directly growing 2D PtSe2 layers of controlled orientation on polyimide polymeric substrates and fabricating their Kirigami structures, further strengthening the application potential of this material. Discussions on the growth mechanism behind the horizontal-to-vertical 2D layer transition are also presented.

Two-dimensional transition-metal dichalcogenide (2D TMD) layers are highly attractive for emerging stretchable and foldable electronics owing to their extremely small thickness coupled with extraordinary electrical and optical properties. Although intrinsically large strain limits are projected in them (i.e., several times greater than silicon), integrating 2D TMDs in their pristine forms does not realize superior mechanical tolerance greatly demanded in high-end stretchable and foldable devices of unconventional form factors. In this article, we report a versatile and rational strategy to convert 2D TMDs of limited mechanical tolerance to tailored 3D structures with extremely large mechanical stretchability accompanying well-preserved electrical integrity and modulated transport properties. We employed a concept of strain engineering inspired by an ancient paper-cutting art, known as kirigami patterning, and developed 2D TMD-based kirigami electrical conductors. Specifically, we directly integrated 2D platinum diselenide (2D PtSe2) layers of controlled carrier transport characteristics on mechanically flexible polyimide (PI) substrates by taking advantage of their low synthesis temperature. The metallic 2D PtSe2/PI kirigami patterns of optimized dimensions exhibit an extremely large stretchability of ∼2000% without compromising their intrinsic electrical conductance. They also present strain-tunable and reversible photoresponsiveness when interfaced with semiconducting carbon nanotubes (CNTs), benefiting from the formation of 2D PtSe2/CNT Schottky junctions. Moreover, kirigami field-effect transistors (FETs) employing semiconducting 2D PtSe2 layers exhibit tunable gate responses coupled with mechanical stretching upon electrolyte gating. The exclusive role of the kirigami pattern parameters in the resulting mechanoelectrical responses was also verified by a finite-element modeling (FEM) simulation. These multifunctional 2D materials in unconventional yet tailored 3D forms are believed to offer vast opportunities for emerging electronics and optoelectronics.

While many technologies rely on multilayer heterostructures, most of the studies on chemical functionalization have been limited to monolayer graphene. In order to use functionalization in multilayer systems, we must first understand the interlayer interactions between functionalized and nonfunctionalized (intact) layers and how to selectively functionalize one layer at a time. Here, we demonstrate a method to fabricate single- or double-sided fluorinated bilayer graphene (FBG) by tailoring substrate interactions. Both the top and bottom surfaces of bilayer graphene on the rough silicon dioxide (SiO2) are fluorinated; meanwhile, only the top surface of graphene on hexagonal boron nitride (hBN) is fluorinated. The functionalization type affects electronic properties; double-sided FBG on SiO2 is insulating, whereas single-sided FBG on hBN maintains conducting, showing that the intact bottom layer becomes electrically decoupled from the fluorinated top insulating layer. Our results define a straightforward method to selectively functionalize the top and bottom surfaces of bilayer graphene.

Since the isolation of graphene, various two-dimensional (2D) materials have been extensively investigated. Nevertheless, only few 2D oxides have been reported to date due to difficulties in their synthesis. However, it is expected that the layered transition-metal oxides (TMOs) could be missing blocks for van der Waals heterostructures and essential elements for 2D electronics. Herein, the crystal structure and band structure of van der Waals epitaxially grown α-MoO3 nanosheets on various 2D growth templates are characterized. Monolayer and multilayer α-MoO3 nanosheets are successfully grown on a 2D substrate by simply evaporating amorphous molybdenum oxide thin film in ambient conditions. A single-crystal α-MoO3 nanosheet without grain boundary is epitaxially grown on various 2D substrates despite a large lattice mismatch. During growth, the quasi-stable monolayer α-MoO3 first covers the 2D substrate, then additional layers are continuously grown on the first monolayer α-MoO3. The band gap of the α-MoO3 increases from 2.9 to 3.2 eV as the thickness decreases. Furthermore, due to oxygen vacancies and surface adsorbates, the synthesized α-MoO3 is highly n-doped with a small work function. Therefore, α-MoO3 field-effect transistors (FETs) exhibit a typical n-type conductance. This work shows the great potential of ultra-thin α-MoO3 in 2D-material-based electronics.

Two-dimensional molybdenum disulfide (2D MoS2) presents extraordinary optical, electrical, and chemical properties which are highly tunable by engineering the orientation of constituent 2D layers. 2D MoS2 films with vertically-aligned layers exhibit numerous 2D edge sites which are predicted to offer superior chemical reactivity owing to their enriched dangling bonds. This enhanced chemical reactivity coupled with their tunable band gap energy can render the vertical 2D MoS2 unique opportunities for environmental applications that go beyond the conventional applications of horizontal 2D MoS2 in electronics/opto-electronics. Herein, we report that MoS2 films with vertically-aligned 2D layers exhibit excellent visible light responsive photocatalytic activities for efficiently degrading organic compounds in contaminated water such as harmful algal blooms. We demonstrate the visible light-driven rapid degradation of microcystin-LR, one of the most toxic compounds produced by the algal blooms, and reveal that the degradation efficiency can be significantly improved by incorporating noble metals. This study suggests a high promise of these emerging 2D materials for water treatment, significantly broadening their versatility for a wide range of energy and environmental applications.