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Register a new userImproved chemical vapor transport growth of transition metal dichalcogenides
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In the crystal growth of transition metal dichalcogenides by the Chemical Vapor Transport method (CVT), the choice of the transport agent plays a key role. We have investigated the effect of various chemical elements and compounds on the growth of TiSe2, MoSe2, TaS2 and TaSe2 and found that pure I2 is the most suitable for growing TiSe2, whereas transition metal chlorides perform best with Mo- and Ta- chalcogenides. The use of TaCl5 as a transport agent in the CVT process allows to selectively growth either polymorph of TaS2 and TaSe2 and the optimum growth conditions are reported. Moreover, by using TaCl5 and tuning the temperature and the halogen starting ratio, it was possible to grow whiskers of the compounds TaS2, TaSe2, TaTe2, TaS3 and TaSe3.
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Transition metal dichalcogenides (TMDs) are van der Waals layered materials with sizable and tunable bandgaps, offering promising platforms for two-dimensional electronics and optoelectronics. To this end, the bottleneck is how to acquire high-quality single crystals in a facile and efficient manner. As one of the most widely employed method of single-crystal growth, conventional chemical vapor transport (CVT) generally encountered problems including the excess nucleation that leads to small crystal clusters and slow growth rate. To address these issues, a seed crystal is introduced to suppress the nucleation and an inner tube is adopted as both a separator and a flow restrictor, favoring the growth of large-size and high-quality TMD single crystals successfully. Three examples are presented, the effective growth of millimeter-sized MoSe2 and MoTe2 single crystals, and the greatly shortened growth period for PtSe2 single crystal, all of which are synthesized in high quality according to detailed characterizations. The mechanism of seeded CVT is discussed. Furthermore, a phototransistor based on exfoliated multi-layered MoSe2 displays excellent photoresponse in ambient conditions, and considerably rapid rise and fall time of 110 and 125 us are obtained. This work paves the way for developing a facile and versatile method to synthesize high-quality TMD single crystals in laboratory, which could serve as favorable functional materials for potential low-dimensional optoelectronics.
The usage of molten salts, e.g., Na2MoO4 and Na2WO4, has shown great success in the growth of two-dimensional (2D) transition metal dichalcogenides (TMDCs) by chemical vapor deposition (CVD). In comparison with the halide salt (i.e., NaCl, NaBr, KI)-assisted growth (Salt 1.0), the molten salt-assisted vapor-liquid-solid (VLS) growth technique (Salt 2.0) has improved the reproducibility, efficiency and scalability of synthesizing 2D TMDCs. However, the growth of large-area MoSe2 and WTe2 is still quite challenging with the use Salt 2.0 technique. In this study, a renewed Salt 2.0 technique using mixed salts (e.g., Na2MoO4-Na2SeO3 and Na2WO4-Na2TeO3) is developed for the enhanced CVD growth of 2D MoSe2 and WTe2 crystals with large grain size and yield. Continuous monolayer MoSe2 film with grain size of 100-250 {mu}m or isolated flakes up to ~ 450 {mu}m is grown on a halved 2-inch SiO2/Si wafer. Our study further confirms the synergistic effect of Na+ and SeO32- in the enhanced CVD growth of wafer-scale monolayer MoSe2 film. And thus, the addition of Na2SeO3 and Na2TeO3 into the transition metal salts could be a general strategy for the enhanced CVD growth of many other 2D selenides and tellurides.
Due to their physical properties and potential applications in energy conversion and storage, transition metal dichalcogenides (TMDs) have garnered substantial interest in recent years. Amongst this class of materials, TMDs based on molybdenum, tungsten, sulfur and selenium are particularly attractive due to their semiconducting properties and the availability of bottom-up synthesis techniques. Here we report a method which yields high quality crystals of transition metal diselenide and ditelluride compounds (PtTe2, PdTe2, NiTe2, TaTe2, TiTe2, RuTe2, PtSe2, PdSe2, NbSe2, TiSe2, VSe2, ReSe2) from their solid solutions, via vapor deposition from a metal-saturated chalcogen melt. Additionally, we show the synthesis of rare-earth metal poly-chalcogenides and NbS2 crystals using the aforementioned process. Most of the obtained crystals have a layered CdI2 structure. We have investigated the physical properties of selected crystals and compared them to state-of-the-art findings reported in the literature. Remarkably, the charge density wave transition in 1T-TiSe2 and 2H-NbSe2 crystals is well-defined at TCDW ~ 200 K and ~ 33 K, respectively. Angle-resolved photoelectron spectroscopy and electron diffraction are used to directly access the electronic and crystal structures of PtTe2 single crystals, and yield state-of-the-art measurements.
Starting from graphene, 2D layered materials family has been recently set up more than 100 different materials with variety of different class of materials such as semiconductors, metals, semimetals, superconductors. Among these materials, 2D semiconductors have found especial importance in the state of the art device applications compared to that of the current conventional devices such as (which material based for example Si based) field effect transistors (FETs) and photodetectors during the last two decades. This high potential in solid state devices is mostly revealed by the transition metal dichalcogenides (TMDCs) semiconductor materials such as MoS2 , WS2 , MoSe2 and WSe2 . Therefore, many different methods and approaches have been developed to grow or obtain so far in order to make use them in solid state devices, which is a great challenge in large area applications. Although there are intensively studied methods such as chemical vapor deposition (CVD), mechanical exfoliation, atomic layer deposition, it is sputtering getting attention day by day due to the simplicity of the growth method together with its reliability, large area growth possibility and repeatability. In this review article, we provide benefits and disadvantages of all the growth methods when growing TMDC materials, then focusing on the sputtering TMDC growth strategies performed. In addition, TMDCs for the FETs and photodetector devices grown by RFMS have been surveyed.
Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted much interest and shown promise in many applications. However, it is challenging to obtain uniform TMDCs with clean surfaces, because of the difficulties in controlling the way the reactants are supplied to the reaction in the current chemical vapor deposition (CVD) growth process. Here, we report a new growth approach called dissolution-precipitation (DP) growth, where the metal sources are sealed inside glass substrates to control their feeding to the reaction. Noteworthy, the diffusion of metal source inside glass to its surface provides a uniform metal source on the glass surface, and restricts the TMDC growth to only a surface reaction while eliminates unwanted gas-phase reaction. This feature gives rise to highly-uniform monolayer TMDCs with a clean surface on centimeter-scale substrates. The DP growth works well for a large variety of TMDCs and their alloys, providing a solid foundation for the controlled growth of clean TMDCs by the fine control of the metal source.
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