Activating a Two-Dimensional PtSe2 Basal Plane for the Hydrogen Evolution Reaction through the Simultaneous Generation of Atomic Vacancies and Pt Clusters.

Two-dimensional (2D) PtSe2 has emerged as a promising ultrathin electrocatalyst due to its excellent catalytic activity and conductivity. However, the PtSe2 basal plane is inert for the hydrogen evolution reaction (HER), which greatly limits its electrocatalytic performance. Here, in light of theoretical calculations, we designed a facile approach for activating the 2D PtSe2 basal plane for the HER by simultaneously introducing atomic vacancies of Se, Pt, and Pt clusters through a mild Ar plasma treatment. We tracked changes in the structures and catalytic performance of PtSe2 by combining microscopic imaging, spectroscopic mapping, and electrochemical measurements in microcells. The highest performance of the activated PtSe2 basal plane that we obtained was superior to those of other 2D transition metal dichalcogenide-based electrocatalysts measured in microcells in terms of the overpotential, the Tafel slope, and the exchange current density. This study demonstrates the great potential of activated 2D PtSe2 as an ultrathin catalyst for the HER and provides new insights on the rational design of 2D electrocatalysts.

Unveiling the Layer-Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction.

Two-dimensional (2D) PtSe2 shows the most prominent layer-dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure-activity correlations in 2D systems. Here, starting with the synthesis of single-crystalline 2D PtSe2 with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer-dependent HER catalytic activity of 2D PtSe2 from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe2 flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure-activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.

Two-Dimensional Semiconductors Grown by Chemical Vapor Transport.

Developing controlled approaches for synthesizing high-quality two-dimensional (2D) semiconductors is essential for their practical applications in novel electronics. The application of chemical vapor transport (CVT), an old single-crystal growth technique, has been extended from growing 3D crystals to synthesizing 2D atomic layers by tuning the growth kinetics. Both single crystalline individual flakes and continuous films of 1 L MoS2 were successfully obtained with CVT approach at low growth temperatures of 300-600 °C. The obtained 1 L MoS2 exhibits high crystallinity and comparable mobility to mechanically exfoliated samples, as confirmed by both atomic resolution microscopic imaging and electrical transport measurements. Besides MoS2 , this method was also used in the growth of 2D WS2 , MoSe2 , Mox W1-x S2 alloys, and ReS2 , thus opening up a new way for the controlled synthesis of various 2D semiconductors.

Controlled Synthesis of Two-Dimensional 1T-TiSe2 with Charge Density Wave Transition by Chemical Vapor Transport.

Two-dimensional (2D) metallic transition metal dichalcogenides (TMDCs), such as 1T-TiSe2, are ideal systems for exploring the fundamentals in condensed matter physics. However, controlled synthesis of these ultrathin materials has not been achieved. Here, we explored the synthesis of charge density wave (CDW)-bearing 2D TiSe2 with chemical vapor transport (CVT) by extending this bulk crystal growth approach to the surface growth of TiSe2 by introducing suitable growth substrates and dramatically slowing down the growth rate. Sub-10 nm TiSe2 flakes were successfully obtained, showing comparable quality to the mechanically exfoliated thin flakes. A CDW state with 2 × 2 superstructure was clearly observed on these ultrathin flakes by scanning tunneling microscopy (STM), and the phase transition temperature of these flakes was investigated by transport measurements, confirming the existence of CDW states. Our work opens up a new approach to synthesizing 2D CDW and superconductive TMDCs for exploring new fundamentals and applications in novel electronics.

Chemical Synthesis and Integration of Highly Conductive PdTe2 with Low-Dimensional Semiconductors for p-Type Transistors with Low Contact Barriers.

Low-dimensional semiconductors provide promising ultrathin channels for constructing more-than-Moore devices. However, the prominent contact barriers at the semiconductor-metal electrodes interfaces greatly limit the performance of the obtained devices. Here, a chemical approach is developed for the construction of p-type field-effect transistors (FETs) with low contact barriers by achieving the simultaneous synthesis and integration of 2D PdTe2 with various low-dimensional semiconductors. The 2D PdTe2 synthesized through a quasi-liquid process exhibits high electrical conductivity (≈4.3 × 106 S m-1 ) and thermal conductivity (≈130 W m-1 K-1 ), superior to other transition metal dichalcogenides (TMDCs) and even higher than some metals. In addition, PdTe2 electrodes with desired geometry can be synthesized directly on 2D MoTe2 and other semiconductors to form high-performance p-type FETs without any further treatment. The chemically derived atomically ordered PdTe2 -MoTe2 interface results in significantly reduced contact barrier (65 vs 240 meV) and thus increases the performance of the obtained devices. This work demonstrates the great potential of 2D PdTe2 as contact materials and also opens up a new avenue for the future device fabrication through the chemical construction and integration of 2D components.