Phase Engineering of Nanomaterials: Transition Metal Dichalcogenides.

Crystal phase, a critical structural characteristic beyond the morphology, size, dimension, facet, etc., determines the physicochemical properties of nanomaterials. As a group of layered nanomaterials with polymorphs, transition metal dichalcogenides (TMDs) have attracted intensive research attention due to their phase-dependent properties. Therefore, great efforts have been devoted to the phase engineering of TMDs to synthesize TMDs with controlled phases, especially unconventional/metastable phases, for various applications in electronics, optoelectronics, catalysis, biomedicine, energy storage and conversion, and ferroelectrics. Considering the significant progress in the synthesis and applications of TMDs, we believe that a comprehensive review on the phase engineering of TMDs is critical to promote their fundamental studies and practical applications. This Review aims to provide a comprehensive introduction and discussion on the crystal structures, synthetic strategies, and phase-dependent properties and applications of TMDs. Finally, our perspectives on the challenges and opportunities in phase engineering of TMDs will also be discussed.

Phase-Controlled Growth of 1T'-MoS2 Nanoribbons on 1H-MoS2 Nanosheets.

2D heterostructures are emerging as alternatives to conventional semiconductors, such as silicon, germanium, and gallium nitride, for next-generation electronics and optoelectronics. However, the direct growth of 2D heterostructures, especially for those with metastable phases still remains challenging. To obtain 2D transition metal dichalcogenides (TMDs) with designed phases, it is highly desired to develop phase-controlled synthetic strategies. Here, a facile chemical vapor deposition method is reported to prepare vertical 1H/1T' MoS2 heterophase structures. By simply changing the growth atmosphere, semimetallic 1T'-MoS2 can be in situ grown on the top of semiconducting 1H-MoS2 , forming vertical semiconductor/semimetal 1H/1T' heterophase structures with a sharp interface. The integrated device based on the 1H/1T' MoS2 heterophase structure displays a typical rectifying behavior with a current rectifying ratio of ≈103 . Moreover, the 1H/1T' MoS2 -based photodetector achieves a responsivity of 1.07 A W-1 at 532 nm with an ultralow dark current of less than 10-11 A. The aforementioned results indicate that 1H/1T' MoS2 heterophase structures can be a promising candidate for future rectifiers and photodetectors. Importantly, the approach may pave the way toward tailoring the phases of TMDs, which can help us utilize phase engineering strategies to promote the performance of electronic devices.

Reversible Semimetal-Semiconductor Transition of Unconventional-Phase WS2 Nanosheets.

Phase transition with band gap modulation of materials has gained intensive research attention due to its various applications, including memories, neuromorphic computing, and transistors. As a powerful strategy to tune the crystal phase of transition-metal dichalcogenides (TMDs), the phase transition of TMDs provides opportunities to prepare new phases of TMDs for exploring their phase-dependent property, function, and application. However, the previously reported phase transition of TMDs is mainly irreversible. Here, we report a reversible phase transition in the semimetallic 1T'-WS2 driven by proton intercalation and deintercalation, resulting in a newly discovered semiconducting WS2 with a novel unconventional phase, denoted as the 1T'd phase. Impressively, an on/off ratio of >106 has been achieved during the phase transition of WS2 from the semimetallic 1T' phase to the semiconducting 1T'd phase. Our work not only provides a unique insight into the phase transition of TMDs via proton intercalation but also opens up possibilities to tune their physicochemical properties for various applications.

Salt-Assisted 2H-to-1T' Phase Transformation of Transition Metal Dichalcogenides.

Phase engineering of nanomaterials (PEN) has demonstrated great potential in the fields of catalysis, electronics, energy storage and conversion, and condensed matter physics. Recently, transition metal dichalcogenides (TMDs) with unconventional metastable phases (e.g., 1T and 1T') have attracted increasing research interest due to their unique and appealing physicochemical properties. However, there is still a lack of a simple, universal, and controlled method for the preparation of large-scale and high-purity unconventional-phase TMD crystals, restricting their further fundamental study and practical applications. Here, a facile, one-step salt-assisted general strategy is reported for the controlled phase transformation of commercially available TMDs with conventional 2H phase, yielding a large amount of metastable 1T'-phase TMDs, including WS2 , WSe2 , MoS2 , and MoSe2 . It is found that the easily accessible metal salts, such as K2 C2 O4 ·H2 O, K2 CO3 , Na2 CO3 , Rb2 CO3 , Cs2 CO3 , KHCO3 , NaHCO3 , and NaC2 O4 , can be used to assist the 2H-to-1T' phase transformation, greatly simplifying the synthetic process for producing metastable 1T'-TMDs. Importantly, this method can also be used to prepare 1T'-TMD alloys, such as 1T'-WS2 x Se2(1- x ) . This newly developed strategy is robust and highly effective, which can also be used for the phase engineering of other materials with various polymorphs.