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 μm or isolated flakes up to ~ 450 μm 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.
We report one-pot chemical vapor deposition (CVD) growth of large-area Janus SeMoS monolayers, with the asymmetric top (Se) and bottom (S) chalcogen atomic planes with respect to the central transition metal (Mo) atoms. The formation of these two-dimensional semiconductor monolayers takes place upon the thermodynamic equilibrium-driven exchange of the bottom Se atoms of the initially grown MoSe2 single crystals on gold foils with S atoms. The growth process is characterized by complementary experimental techniques including Raman and X-ray photoelectron spectroscopy and the growth mechanisms a…
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 suppres…
We report on a modified chemical vapor transport (CVT) methodology for the growth of pure and intercalated Zr, Ti, and Hf dichalcogenide single crystals, e.g. ZrTe2, Gd0.05ZrTe2, HfTe2, and Cu0.05TiTe2. While the most common method for CVT growth is carried out in quartz tubes subjected to a temperature gradient between the charge and the growth location, the growth using this isothermal-CVT (ICVT) method takes place isothermally in sealed quartz tubes placed horizontally in box furnaces, using iodine (I2) as the transport agent. The structure and composition of crystals were determined by mea…
The growth of single crystals of MoS2 and WS2 by materials transport through a liquid salt flux made from a low melting mixture of NaCl and CsCl is described. The crystals are characterized by single crystal X-ray diffraction, which reveals that they are 2H-MoS2 with a small percentage (about 3%) of 3R intergrowths. The 2H-WS2 crystals display less than 1% of 3R intergrowths. Photoluminescence spectra of exfoliated monolayers suggest that MoS2 grown by this method has superior crystallinity in comparison to commercially-available MoS2 crystals.
Inhomogeneity of ion correlation widely exists in many physicochemical, soft matter, and biological systems. Here, we apply the modified Gaussian renormalized fluctuation theory to study the classic example of the vapor-liquid interface of ionic fluids. The ion correlation is decomposed into a short-range contribution associated with the local electrostatic environment and a long-range contribution accounting for the spatially varying ionic strength and dielectric permittivity. For symmetric salt, both the coexistence curve and the interfacial tension predicted by our theory are in quantitativ…
Two-dimensional (2D) transition metal dichalcogenides (TMDCs) with unique electrical properties are fascinating materials used for future electronics. However, the strong Fermi level pinning effect at the interface of TMDCs and metal electrodes always leads to high contact resistance, which seriously hinders their application in 2D electronics. One effective way to overcome this is to use metallic TMDCs or transferred metal electrodes as van der Waals (vdW) contacts. Alternatively, using highly conductive doped TMDCs will have a profound impact on the contact engineering of 2D electronics. Her…
The vapor phase synthesis of two-dimensional transition-metal dichalcogenides (MX2) and their heterostructures is often poorly reproducible and sensitive to uncontrolled environmental humidity. It was recently realized that water vapor can play important roles in the growth of MX2 by reacting with MX2 at high temperature to form volatile metal oxyhydroxide (MOx(OH)y) and hydrogen chalcogenides (H2X) that dramatically change the growth processes. Here we report the controllable synthesis of WS2, MoS2, and their heterostructures using water-assisted chemical vapor transport (CVT). The water vapo…
Transition metal dichalcogenide (TMD) monolayers and heterostructures have emerged as a compelling class of materials with transformative new science that may be harnessed for novel device technologies. These materials are commonly fabricated by exfoliation of flakes from bulk crystals, but wafer-scale epitaxy of single crystal films is required to advance the field. This article reviews the fundamental aspects of epitaxial growth of van der Waals bonded crystals specific to TMD films. The structural and electronic properties of TMD crystals are initially described along with sources and metho…
Optical and electrical properties of two-dimensional transition metal dichalcogenides (TMDCs) grown by chemical vapor deposition (CVD) are strongly determined by their microstructure. Consequently, the visualization of spatial structural variations is of paramount importance for future applications. Here we demonstrate how grain boundaries, crystal orientation, and strain fields can unambiguously be identified with combined lateral force microscopy (LFM) and transverse shear microscopy (TSM) for CVD-grown tungsten disulfide (WS2) monolayers, on length scales that are relevant for optoelectroni…
Innovative applications based on two-dimensional solids require cost-effective fabrication processes resulting in large areas of high quality materials. Chemical vapour deposition is among the most promising methods to fulfill these requirements. However, for 2D materials prepared in this way it is generally assumed that they are of inferior quality in comparison to the exfoliated 2D materials commonly used in basic research. In this work we challenge this assumption and aim to quantify the differences in quality for the prototypical transition metal dichalcogenide MoS$_2$. To this end single …
A novel procedure, based in a closed space vapor transport (CSVT) configuration, has been devised to grow films or flakes of pure MoO2 in a reductive atmosphere, at relatively low temperature and using MoO3 as the source. In contrast with conventional CSVT technique, in the proposed method a temperature gradient is not required for the growth to take place, which occurs through an intermediate volatile transport species that is produced in the complex reduction reaction of MoO3. An added value of this simple method is the possibility of transforming the MoO2 into MoTe2, one of the most interes…
Chemical vapor deposition (CVD) is a powerful method employed for high quality monolayer crystal growth of 2D transition metal dichalcogenides with much effort invested toward improving the growth process. Here, we report a novel method for CVD based growth of monolayer molybdenum disulfide (MoS2) by using thermally evaporated thin films of molybdenum trioxide (MoO3) as the molybdenum (Mo) source for co-evaporation. Uniform evaporation rate of the MoO3 thin films provides uniform Mo vapor which promotes highly reproducible single crystal growth of MoS2 throughout the substrate. These high-qual…
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 …
Transition metal dichalcogenides (TMDs) display a rich variety of instabilities such as spin and charge orders, Ising superconductivity and topological properties. Their physical properties can be controlled by doping in electric double-layer field-effect transistors (FET). However, for the case of single layer NbSe$_2$, FET doping is limited to $\approx 1\times 10^{14}$ cm$^{-2}$, while a somewhat larger charge injection can be obtained via deposition of K atoms. Here, by performing ARPES, STM, quasiparticle interference measurements, and first principles calculations we show that a misfit co…
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) fr…
Vapor transportation is the core process in growing transition-metal dichalcogenides (TMDCs) by chemical vapor deposition (CVD). One inevitable problem is the spatial inhomogeneity of the vapors. The non-stoichiometric supply of transition-metal precursors and chalcogen leads to poor control in products' location, morphology, crystallinity, uniformity and batch to batch reproducibility. While vapor-liquid-solid (VLS) growth involves molten precursors at the growth temperatures higher than their melting points. The liquid sodium molybdate can precipitate solid MoS2 monolayers when saturated wit…
Universal effect of ammonia pressure on synthesis of colloidal metal nitrides in molten salts
Pritzker School of Molecular Engineering, University of Chicago（芝加哥大学普里茨克分子工程学院）；Interdisciplinary Materials Science Program, Vanderbilt University（范德堡大学交叉材料科学项目）；Department of Chemistry and James Franck Institute, University of Chicago（芝加哥大学化学系和詹姆斯·弗兰克研究所）；Department of Chemistry, Northwestern University（西北大学化学系）；Center for Nanoscale Materials, Argonne National Laboratory（阿贡国家实验室纳米材料中心）；Department of Chemical and Biomolecular Engineering, Vanderbilt University（范德堡大学化学与生物分子工程系）
Theoretical calculations and experimental observations show MoTe2 is a type II Weyl semimetal, along with many members of transition metal dichalcogenides family. We have grown highly crystalline large-area MoTe2 thin films on Si/SiO2 substrates by chemical vapor deposition. Very uniform, continuous, and smooth films were obtained as confirmed by scanning electron microscopy and atomic force microscopy analyses. Measurements of the temperature dependence of longitudinal resistivity and current-voltage characteristics at different temperature are discussed. Unsaturated, positive quadratic magne…
Great achievements have been made in alloying of two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs), which can allow tunable band gaps for practical applications in optoelectronic devices. However, telluride-based TMDs alloys were less studied due to the difficulties of sample synthesis. Here, in this work we report the large-area synthesis of 2D MoTexSe2-x alloy films with controllable Te composition by a modified alkali metal halides assisted chemical vapor deposition method. The as-prepared films have millimeter-scale transverse size. Raman spectra experiments combi…
The electronic and optoelectronic properties of two dimensional materials have been extensively explored in graphene and layered transition metal dichalcogenides (TMDs). Spintronics in these two-dimensional materials could provide novel opportunities for future electronics, for example, efficient generation of spin current, which should enable the efficient manipulation of magnetic elements. So far, the quantitative determination of charge current induced spin current and spin-orbit torques (SOTs) on the magnetic layer adjacent to two-dimensional materials is still lacking. Here, we report a l…
Two-dimensional materials such as transitional metal dichalcogenides exhibit unique optical and electrical properties. Here we report on the varying optical properties of CVD grown MoS2 monolayer flakes with different shapes. In particular, it is observed that the perimeter and the central region of the flakes have non-uniform photoluminescence (PL) energy and intensity. We quantified these effects systematically and propose that thermally induced strain during growth is the origin. The strain relaxation after transfer of the MoS2 flakes supports this explanation. Detailed investigations of th…
Metal organic chemical vapor deposition (MOCVD) is one of the main methodologies used for thin film fabrication in the semiconductor industry today and is considered one of the most promising routes to achieve large-scale and high-quality 2D transition metal dichalcogenides (TMDCs). However, if not taken special measures, MOCVD suffers from some serious drawbacks, such as small domain size and carbon contamination, resulting in poor optical and crystal quality, which may inhibit its implementation for the large-scale fabrication of atomic-thin semiconductors. Here we present a Growth-Etch MOCV…
Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted great attention due to their physical and chemical properties that make them promising in electronics and optoelectronics. Because of the difficulties in controlling concentrations of solid precursors and spatially non-uniform growth dynamics, it is challenging to grow wafer-scale 2D TMDCs with good uniformity and reproducibility so far, which significantly hinders their practical use. Here we report a vertical chemical vapor deposition (VCVD) design to grow monolayer TMDCs with a uniform density and high quality over…
Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDs), such as MoS$_2$, are promising candidates for nanoscale photonics because of strong-light matter interactions. However, Fermi level pinning due to metal-induced gap (MIGS) states at the metals-monolayer MoS$_2$ interface limits the application of optoelectronic devices based on conventional metals because of the high contact resistance of the Schottky contacts. On the other hand, a semimetal-TMD-semimetal device can overcome this limitation, where the MIGS are sufficiently suppressed and can result in ohmic contacts.…
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 me…
Chemical vapor deposition (CVD) allows growing transition metal dichalcogenides (TMDs) over large surface areas on inexpensive substrates. In this work, we correlate the structural quality of CVD grown MoS$_2$ monolayers (MLs) on SiO$_2$/Si wafers studied by high-resolution transmission electron microscopy (HRTEM) with high optical quality revealed in optical emission and absorption from cryogenic to ambient temperatures. We determine a defect concentration of the order of 10$^{13}$ cm$^{-2}$ for our samples with HRTEM. To have access to the intrinsic optical quality of the MLs, we remove the …
Dielectrics are insulating materials used in many different electronic devices and play an important role in all of them. Current advanced electronic devices use dielectric materials with a high dielectric constant and avoid high leakage currents. However, these materials show several intrinsic problems, and also a bad interaction with adjacent materials. Therefore, the race for finding a suitable dielectric material for current and future electronic devices is still open. In this context two dimensional [2D] materials have become a serious option, not only thanks to their advanced properties,…
Achieving large-size two-dimensional (2D) crystals is key to fully exploiting their remarkable functionalities and application potentials. Chemical vapor deposition (CVD) growth of 2D semiconductors such as monolayer MoS2 has been reported to be activated by halide salts, yet clear identification of the underlying mechanism remains elusive. Here we provide unambiguous experimental evidence showing that the MoS2 growth dynamics are halogen-dependent through the Brønsted-Evans-Polanyi relation, based on which we build a growth model by considering MoS2 edge passivation by halogens, and theoretic…
