Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe2 Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy.

PdSe2 has a layered structure with an unusual, puckered Cairo pentagonal tiling. Its atomic bond configuration features planar 4-fold-coordinated Pd atoms and intralayer Se-Se bonds that enable polymorphic phases with distinct electronic and quantum properties, especially when atomically thin. PdSe2 is conventionally orthorhombic, and direct synthesis of its metastable polymorphic phases is still a challenge. Here, we report an ambient-pressure chemical vapor deposition approach to synthesize metastable monoclinic PdSe2. Monoclinic PdSe2 is shown to be synthesized selectively under Se-deficient conditions that induce Se vacancies. These defects are shown by first-principles density functional theory calculations to reduce the free energy of the metastable monoclinic phase, thereby stabilizing it during synthesis. The structure and composition of the monoclinic PdSe2 crystals are identified and characterized by scanning transmission electron microscopy imaging, convergent beam electron diffraction, and electron energy loss spectroscopy. Polarized Raman spectroscopy of the monoclinic PdSe2 flakes reveals their strong in-plane optical anisotropy. Electrical transport measurements show that the monoclinic PdSe2 exhibits n-type charge carrier conduction with electron mobilities up to ∼298 cm2 V-1 s-1 and a strong in-plane electron mobility anisotropy of ∼1.9. The defect-mediated growth pathway identified in this work is promising for phase-selective direct synthesis of other 2D transition metal dichalcogenides.

Low Energy Implantation into Transition-Metal Dichalcogenide Monolayers to Form Janus Structures.

Atomically thin two-dimensional (2D) materials face significant energy barriers for synthesis and processing into functional metastable phases such as Janus structures. Here, the controllable implantation of hyperthermal species from pulsed laser deposition (PLD) plasmas is introduced as a top-down method to compositionally engineer 2D monolayers. The kinetic energies of Se clusters impinging on suspended monolayer WS2 crystals were controlled in the <10 eV/atom range with in situ plasma diagnostics to determine the thresholds for selective top layer replacement of sulfur by selenium for the formation of high quality WSSe Janus monolayers at low (300 °C) temperatures and bottom layer replacement for complete conversion to WSe2. Atomic-resolution electron microscopy and spectroscopy in tilted geometry confirm the WSSe Janus monolayer. Molecular dynamics simulations reveal that Se clusters implant to form disordered metastable alloy regions, which then recrystallize to form highly ordered structures, demonstrating low-energy implantation by PLD for the synthesis of 2D Janus layers and alloys of variable composition.

Two-Dimensional Palladium Diselenide with Strong In-Plane Optical Anisotropy and High Mobility Grown by Chemical Vapor Deposition.

Two-dimensional (2D) palladium diselenide (PdSe2 ) has strong interlayer coupling and a puckered pentagonal structure, leading to remarkable layer-dependent electronic structures and highly anisotropic in-plane optical and electronic properties. However, the lack of high-quality, 2D PdSe2 crystals grown by bottom-up approaches limits the study of their exotic properties and practical applications. In this work, chemical vapor deposition growth of highly crystalline few-layer (≥2 layers) PdSe2 crystals on various substrates is reported. The high quality of the PdSe2 crystals is confirmed by low-frequency Raman spectroscopy, scanning transmission electron microscopy, and electrical characterization. In addition, strong in-plane optical anisotropy is demonstrated via polarized Raman spectroscopy and second-harmonic generation maps of the PdSe2 flakes. A theoretical model based on kinetic Wulff construction theory and density functional theory calculations is developed and described the observed evolution of "square-like" shaped PdSe2 crystals into rhombus due to the higher nucleation barriers for stable attachment on the (1,1) and (1,-1) edges, which results in their slower growth rates. Few-layer PdSe2 field-effect transistors reveal tunable ambipolar charge carrier conduction with an electron mobility up to ≈294 cm2 V-1 s-1 , which is comparable to that of exfoliated PdSe2 , indicating the promise of this anisotropic 2D material for electronics.

Layer-by-Layer Thinning of PdSe2 Flakes via Plasma Induced Oxidation and Sublimation.

Controlled O2/Ar plasma exposure and subsequent low temperature inert atmosphere annealing of chemical vapor deposition (CVD) grown PdSe2 flakes etch PdSe2 layer-by-layer in an atomic layer etching-like (ALE) process. X-ray photoelectron spectroscopy (XPS) shows that exposure to a remote inductively coupled plasma (ICP) oxygen plasma oxidizes the top layer of the PdSe2 to form PdO2 and SeO2. After an in situ annealing, XPS shows no trace of PdO2 or SeO2, suggesting the byproducts are volatile at low temperature. Atomic force microscopy of PdSe2 exposed to various O2 + Ar plasmas (O2 = 25-100%) demonstrates a clear trend between the oxygen concentration and the number of layers etched per cycle. PdSe2 field effect transistors (FETs) were characterized at various stages of two ALE-like cycles, and the electrical properties are correlated to the oxidation and byproduct desorption and layer reduction.

Defect-Mediated Phase Transformation in Anisotropic Two-Dimensional PdSe2 Crystals for Seamless Electrical Contacts.

The failure to achieve stable Ohmic contacts in two-dimensional material devices currently limits their promised performance and integration. Here we demonstrate that a phase transformation in a region of a layered semiconductor, PdSe2, can form a contiguous metallic Pd17Se15 phase, leading to the formation of seamless Ohmic contacts for field-effect transistors. This phase transition is driven by defects created by exposure to an argon plasma. Cross-sectional scanning transmission electron microscopy is combined with theoretical calculations to elucidate how plasma-induced Se vacancies mediate the phase transformation. The resulting Pd17Se15 phase is stable and shares the same native chemical bonds with the original PdSe2 phase, thereby forming an atomically sharp Pd17Se15/PdSe2 interface. These Pd17Se15 contacts exhibit a low contact resistance of ∼0.75 kΩ µm and Schottky barrier height of ∼3.3 meV, enabling nearly a 20-fold increase of carrier mobility in PdSe2 transistors compared to that of traditional Ti/Au contacts. This finding opens new possibilities in the development of better electrical contacts for practical applications of 2D materials.

Layered SnSe nano-plates with excellent in-plane anisotropic properties of Raman spectrum and photo-response.

In-plane anisotropy in optical, electronic and thermal properties of two-dimensional (2D) materials has attracted significant interest because of the huge potential applications for developing novel devices. In this work, outstanding angle-dependent Raman property of layered SnSe nano-plates is obtained via polarized Raman system and it is confirmed that the Raman polarization directions of two Ag modes (130 cm-1 and 150 cm-1) are consistent with specific crystalline directions (zigzag direction or armchair direction) of SnSe flakes under parallel polarization configuration at home temperature and low temperature. Furthermore, the SnSe nano-plate devices show excellent angle-resolved photo-response at home temperature and low temperature (150 K) with a 90° cycle period and the polarized directions are also along zigzag direction and armchair direction, which is ascribed to the unique in-plane asymmetric crystal structure. These prominent in-plane anisotropic properties provide a precise and rapid method to determine the crystal orientation of SnSe nano-flakes and open up the new applications of 2D asymmetric structure materials.

van der Waals epitaxial two-dimensional CdSxSe(1-x) semiconductor alloys with tunable-composition and application to flexible optoelectronics.

Despite the substantial progress in the development of two-dimensional (2D) materials from conventional layered crystals, it still remains particularly challenging to produce high-quality 2D non-layered semiconductor alloys which may bring in some unique properties and new functions. In this work, the synthesis of well-oriented 2D non-layered CdSxSe(1-x) semiconductor alloy flakes with tunable compositions and optical properties is established. Structural analysis reveals that the 2D non-layered alloys follow an incommensurate van der Waals epitaxial growth pattern. Photoluminescence measurements show that the 2D alloys have composition-dependent direct bandgaps with the emission peak varying from 1.8 eV to 2.3 eV, coinciding well with the density functional theory calculations. Furthermore, photodetectors based on the CdSxSe(1-x) flakes exhibit a high photoresponsivity of 703 A W-1 with an external quantum efficiency of 1.94 × 103 and a response time of 39 ms. Flexible devices fabricated on a thin mica substrate display good mechanical stability upon repeated bending. This work suggests a facile and general method to produce high-quality 2D non-layered semiconductor alloys for next-generation optoelectronic devices.