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.

Platinum ditelluride (PtTe2) is an emerging semimetallic two-dimensional (2D) transition-metal dichalcogenide (TMDC) crystal with intriguing band structures and unusual topological properties. Despite much devoted efforts, scalable and controllable synthesis of large-area 2D PtTe2 with well-defined layer orientation has not been established, leaving its projected structure–property relationship largely unclarified. Herein, we report a scalable low-temperature growth of 2D PtTe2 layers on an area greater than a few square centimeters by reacting Pt thin films of controlled thickness with vaporized tellurium at 400 °C. We systematically investigated their thickness-dependent 2D layer orientation as well as its correlated electrical conductivity and surface property. We unveil that 2D PtTe2 layers undergo three distinct growth mode transitions, i.e., horizontally aligned holey layers, continuous layer-by-layer lateral growth, and horizontal-to-vertical layer transition. This growth transition is a consequence of competing thermodynamic and kinetic factors dictated by accumulating internal strain, analogous to the transition of Frank–van der Merwe (FM) to Stranski–Krastanov (SK) growth in epitaxial thin-film models. The exclusive role of the strain on dictating 2D layer orientation has been quantitatively verified by the transmission electron microscopy (TEM) strain mapping analysis. These centimeter-scale 2D PtTe2 layers exhibit layer orientation tunable metallic transports yielding the highest value of ∼1.7 × 106 S/m at a certain critical thickness, supported by a combined verification of density functional theory (DFT) and electrical measurements. Moreover, they show intrinsically high hydrophobicity manifested by the water contact angle (WCA) value up to ∼117°, which is the highest among all reported 2D TMDCs of comparable dimensions and geometries. Accordingly, this study confirms the high material quality of these emerging large-area 2D PtTe2 layers, projecting vast opportunities employing their tunable layer morphology and semimetallic properties from investigations of novel quantum phenomena to applications in electrocatalysis.

Here, we report efficient and stable indium phosphide (InP) based inverted red quantum dot light-emitting diodes (QLEDs) using a new high mobility and deep HOMO level hole transport layer (HTL) and an optimized sol−gel ZnMgO layer. A new hole transport material, DBTA, containing rigid dibenzothiophene and tertiary amine units has been designed with high hole mobility and a deep HOMO level to inject holes faster into the InP-QDs. Also, to decrease the electron transporting property of the ZnMgO NPs, a sol−gel ZnMgO layer with optimum magnesium content (17%), low-temperature annealing (180 °C), and a selfaging process is used on the transparent electrode. The high mobility DBTA and an optimized sol−gel Zn 0.83 Mg 0.17 O layer with the self-aging process are responsible for achieving good charge balance and suppressing nonradiative losses in InP-QLED. The fabricated QLED with DBTA and optimized sol− gel Zn 0.83 Mg 0.17 O exhibited an external quantum efficiency of 21.8%, current efficiency of 23.4 cd/A, and operating lifetime (LT 50 ) of 1095 h at 1000 cd/m 2 .

Two new orange–red thermally activated delayed fluorescence (TADF) materials, PzTDBA and PzDBA, are reported. These materials are designed based on the acceptor–donor–acceptor (A–D–A) configuration, containing rigid boron acceptors and dihydrophenazine donor moieties. These materials exhibit a small ΔEST of 0.05–0.06 eV, photoluminescence quantum yield (PLQY) as high as near unity, and short delayed exciton lifetime (τd) of less than 2.63 µs in 5 wt% doped film. Further, these materials show a high reverse intersystem crossing rate (krisc) on the order of 106 s−1. The TADF devices fabricated with 5 wt% PzTDBA and PzDBA as emitting dopants show maximum EQE of 30.3% and 21.8% with extremely low roll‐off of 3.6% and 3.2% at 1000 cd m−2 and electroluminescence (EL) maxima at 576 nm and 595 nm, respectively. The low roll‐off character of these materials is analyzed by using a roll‐off model and the exciton annihilation quenching rates are found to be suppressed by the fast krisc and short delayed exciton lifetime. These devices show operating device lifetimes (LT50) of 159 and 193 h at 1000 cd m−2 for PzTDBA and PzDBA, respectively. The high efficiency and low roll‐off of these materials are attributed to the good electronic properties originatng from the A–D–A molecular configuration.

Platinum diselenide (PtSe2) is an emerging class of two-dimensional (2D) transition-metal dichalcogenide (TMD) crystals recently gaining substantial interest, owing to its extraordinary properties absent in conventional 2D TMD layers. Most interestingly, it exhibits a thickness-dependent semiconducting-to-metallic transition, i.e., thick 2D PtSe2 layers, which are intrinsically metallic, become semiconducting with their thickness reduced below a certain point. Realizing both semiconducting and metallic phases within identical 2D PtSe2 layers in a spatially well-controlled manner offers unprecedented opportunities toward atomically thin tailored electronic junctions, unattainable with conventional materials. In this study, beyond this thickness-dependent intrinsic semiconducting-to-metallic transition of 2D PtSe2 layers, we demonstrate that controlled plasma irradiation can “externally” achieve such tunable carrier transports. We grew wafer-scale very thin (a few nm) 2D PtSe2 layers by a chemical vapor deposition (CVD) method and confirmed their intrinsic semiconducting properties. We then irradiated the material with argon (Ar) plasma, which was intended to make it more semiconducting by thickness reduction. Surprisingly, we discovered a reversed transition of semiconducting to metallic, which is opposite to the prediction concerning their intrinsic thickness-dependent carrier transports. Through extensive structural and chemical characterization, we identified that the plasma irradiation introduces a large concentration of near-atomic defects and selenium (Se) vacancies in initially stoichiometric 2D PtSe2 layers. Furthermore, we performed density functional theory (DFT) calculations and clarified that the band-gap energy of such defective 2D PtSe2 layers gradually decreases with increasing defect concentration and dimensions, accompanying a large number of midgap energy states. This corroborative experimental and theoretical study decisively verifies the fundamental mechanism for this externally controlled semiconducting-to-metallic transition in large-area CVD-grown 2D PtSe2 layers, greatly broadening their versatility for futuristic electronics.