Films containing 8, 16, 24, 32 and 64 MoSe2 layers were synthesized using the modulated elemental reactants method. X-ray reflectivity patterns showed that the annealed films were the targeted number ...of MoSe2 layers thick with atomically smooth interfaces. In-plane x-ray diffraction (XRD) scans contained only hk0 reflections for crystalline MoSe2 monolayers. Specular XRD patterns contained only 00l reflections, also indicating that the hk0 plane of the MoSe2 layers are parallel to the substrate. Both XRD and electron microscopy techniques indicated that the hk0 planes are rotationally disordered with respect to one another, with all orientations equally probable for large areas. The rotational disorder between MoSe2 layers is present even when analyzed spots are within 10 nm of one another. Cross-plane thermal conductivities of 0.07-0.09 W m−1 K−1 were measured by time domain thermoreflectance, with the thinnest films exhibiting the lowest conductivity. The structural analysis suggests that the ultralow thermal conductivity is a consequence of rotational disorder, which increases the separation between MoSe2 layers. The bonding environment of the Se atoms also becomes significantly distorted from C3v symmetry due to the rotational disorder between layers. This structural disorder efficiently reduces the group velocity of the transverse phonon modes but not that of longitudinal modes. Since rotational disorder between adjacent layers in heterostructures is expected if the constituents have incommensurate lattices, this study indicates that these heterostructures will have very low cross-plane thermal conductivity.
The reaction of ultrathin layers of Mo and Ti with Se was investigated, and significantly different reaction pathways were found. However, in both systems postdeposition annealing results in smooth ...dichalcogenide films with specific thicknesses determined by the precursor. X-ray diffraction (XRD) patterns of as-deposited Mo|Se films around a 1:2 ratio of Mo to Se contain weak, broad reflections from small and isolated MoSe2 crystallites that nucleated during deposition and a sharper intensity maximum resulting from the composition modulation created from the alternating deposition of Mo and Se layers. In contrast, as-deposited Ti|Se films around a 1:2 ratio of Ti to Se contain narrow and intense 00l reflections from TiSe2 crystallites and do not contain a Bragg reflection from the sequence of deposited Ti|Se layers. The as-deposited TiSe2 crystallites have a larger c-axis lattice parameter than was previously reported for TiSe2, however, which suggests a poor vertical interlayer registry and/or high defect densities including interstitial atoms. In-plane XRD patterns show the nucleation of both TiSe2 and Ti2Se during deposition, with the Ti2Se at the substrate. For both systems, annealing the precursors decreases the peak width and increases the intensity of reflections from crystalline TiSe2 and MoSe2. Optimized films consist of a single phase after the annealing and show clear Laue oscillations in the specular XRD patterns, which can only occur if a majority of the diffracting crystallites in the film consist of the same number of unit cells. The highest quality films was obtained when an excess of ∼10% Se was deposited in the precursor, which presumably acts as a flux to facilitate diffusion of metal atoms to crystallite growth fronts and compensates for Se loss to the open system during annealing.
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Heterostructures unconstrained by epitaxy have generated considerable excitement due to the discovery of emergent properties-properties not found in either constituent. Heterostructures enable the ...surfaces on either side of two-dimensional (2D) layers to be used to systematically investigate phenomena such as superconductivity and magnetism in the 2D limit. The ability to choose constituents facilitates the prediction of emergent properties created by the unusual coordination environments at incommensurate interfaces. There have already been many reviews on heterostructures, focusing on a variety of topics that reflect the diverse interest in this area as well as the potential for new technologies. Hence this review focuses mainly on the synthesis and structural characterization of heterostructures containing transition metal dichalcogenides (TMD). This review only briefly discusses 2D materials and TMD/TMD heterostructure devices and the performances that have been achieved. This review provides a historical context for the rapid development of this field and discusses proposed mechanisms for emergent properties. Up to now, the materials used in heterostructures have mainly been materials with 2D structures, as these compounds can be easily cleaved into ultrathin layers. This review discusses the expansion of heterostructure constituents to include materials that do not have 2D structures. Structural changes and charge redistribution between adjacent (or even more distant) layers are likely to be larger for 3D constituents than with 2D constituents based on known misfit layer compounds. Systematic changes in properties with layer thickness, layer sequences, and the identity of constituents will increase our understanding of emergent properties and how they can be optimized.
The composition and thickness of thin films determine their physical properties, making the ability to measure the number of atoms of different elements in films both technologically and ...scientifically important. For thin films, below a certain thickness, the X-ray fluorescence intensity of an element is proportional to the number of atoms. Converting this intensity to the number of atoms per unit area is challenging due to experimental geometries and other correction factors. Hence, the ratio of intensities is more commonly used to determine the composition in terms of element ratios using standards or a model. Here, the number of atoms per unit area was determined using X-ray structure information for over 20 different crystallographically aligned samples with integral unit cell thicknesses. The proportionality constant between intensity and the number of atoms per unit area was determined from linear fits of the background subtracted X-ray fluorescence intensity plotted versus the calculated number of atoms per unit area for each element. The results demonstrate that X-ray fluorescence is very sensitive, capable of measuring changes in the number of atoms of less than 1% of a monolayer for some elements in a variety of sample matrices. Using the calibrated values, an 8 unit cell thick MoSe2 was grown and characterized, demonstrating the usefulness of the ablity to quantify the number of atoms per unit area in a film.
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A significant experimental challenge in testing proposed relationships between structure and properties is the synthesis of targeted structures with atomistic control over both the structure and the ...composition. SnSe2(MoSe2)1.32 was synthesized to test the hypothesis that the low-temperature synthesis of two interleaved structures would result in complete turbostratic disorder and that the disorder would result in ultralow thermal conductivity. SnSe2(MoSe2)1.32 was prepared by depositing elements to form a precursor containing Sn|Se and Mo|Se bilayers, each containing the number of atoms required to form single dichalcogenide planes. The nanoarchitecture of alternating Sn and Mo layers is preserved as the dichalcogenide planes self-assemble at low temperatures. The resulting compound contains well-formed dichalcogenide planes that closely resemble that found in the binary compounds and extensive turbostratic disorder. As expected from proposed structure–property relationships, the thermal conductivity of SnSe2(MoSe2)1.32 is ultralow, ∼0.05 W m–1 K–1.
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The metastable heterostructure, (BiSe)0.97MoSe2, containing alternating bilayers of BiSe and MoSe2 trilayers was synthesized using the modulated elemental reactant method to determine if charge ...transfer from BiSe to MoSe2 would stabilize the metallic 1T polymorph of MoSe2. Optimum synthesis conditions were determined by following the structural evolution as a function of temperature. The structure of the product contained distorted rock salt-structured BiSe layers alternating with hexagonal MoSe2 layers. High-angle annular dark field scanning transmission electron microscopy images revealed that two different polymorphs of MoSe2 coexisted in (BiSe)0.97MoSe2. Raman spectroscopy confirmed the presence of 1T MoSe2 layers. X-ray photoelectron spectroscopy (XPS) indicated that there were two different electronic states for both Mo and Bi. The Mo states are consistent with having octahedral and trigonal prismatic coordination of molybdenum as found in the 1T and 2H polymorphs of MoSe2. The two different electronic states for Bi are consistent with the presence of antiphase boundaries in the BiSe layers. Estimating the relative amount of each electronic state from the XPS spectra indicates that the percentage of 1T MoSe2 is about 40%, whereas the amount of Bi3+ in the BiSe is approximately 60%. The measured resistivity increases as temperature is decreased, consistent with an activated conduction mechanism with a small activation energy (∼0.05 eV). The temperature stability and low resistivity of (BiSe)0.97MoSe2 make it potentially interesting as a means of improving electrical contacts to MoSe2.
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A new approach to the growth of MoSe2 thin films on epitaxial graphene on SiC(0001) by the use of modulated elemental reactants (MER) precursors has been reported. The synthesis applies a two‐step ...process, where first an amorphous precursor is deposited on the substrate which self‐assembles upon annealing. Films with a nominal thickness of about 1 ML are successfully grown on epitaxial graphene monolayer as well as buffer layer samples. Characterization of the films is performed using XPS, LEED, AFM, and Raman spectroscopy. The films are nanocrystalline and show randomly rotated domains. This approach opens up an avenue to synthesize a number of new van‐der‐Waals systems on epitaxial graphene and other substrates.
Two‐dimensional materials are an emerging field in materials science. Methods like MBE and CVD are being used to grow single layers of transition metal dichalcogenides and other materials. In this paper, a novel approach, which employs the deposition of calibrated elemental precursors is presented. Crystalline layers are then formed by self‐assembly of the elemental layers upon annealing. This so‐called modulated elemental reactants (MER) technique has been already established for the synthesis of complex, multilayered 3D heterostructures. Using the model system of MoSe2 on epitaxial graphene on SiC (0001),the 2D level is being targeted.
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