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Simulation and synthesis of alpha-MoCl₃ nanosheets on substrates by short time chemical vapor transport

  • Alpha-molybdenum(III) chloride (MoCl₃) belongs to layered van-der-Waals materials, which are in focus to exhibit interesting properties due to their weak chemical and magnetic interactions. Especially the structure of alpha-MoCl₃ has been discussed in terms of symmetry breaking dimerization of Mo atoms at room temperature, which might led to exotic ground states. By exploiting the 2D materials characteristics, an investigation of physical properties on the nanoscale is intended. We herein demonstrate the probably first approach to synthesize phase pure, as-grown alpha-MoCl₃ few-layer nanosheets by means of a pure short time chemical vapor transport (CVT) process. Vapor growth benefits from a one-step deposition of high crystalline alpha-MoCl₃ nanosheets without stacking faults on a substrate. Thus, mostly applied subsequent delamination, associated with the introduction of structural defects, becomes redundant. According to the CVT process thermodynamic simulations of gas phase equilibria have been performed and the synthesisAlpha-molybdenum(III) chloride (MoCl₃) belongs to layered van-der-Waals materials, which are in focus to exhibit interesting properties due to their weak chemical and magnetic interactions. Especially the structure of alpha-MoCl₃ has been discussed in terms of symmetry breaking dimerization of Mo atoms at room temperature, which might led to exotic ground states. By exploiting the 2D materials characteristics, an investigation of physical properties on the nanoscale is intended. We herein demonstrate the probably first approach to synthesize phase pure, as-grown alpha-MoCl₃ few-layer nanosheets by means of a pure short time chemical vapor transport (CVT) process. Vapor growth benefits from a one-step deposition of high crystalline alpha-MoCl₃ nanosheets without stacking faults on a substrate. Thus, mostly applied subsequent delamination, associated with the introduction of structural defects, becomes redundant. According to the CVT process thermodynamic simulations of gas phase equilibria have been performed and the synthesis conditions could be optimized based on the calculation results. By CVT the as-grown nanolayers are deposited on sapphire (Al₂O₃) substrates by applying a temperature gradient of 70 K from 743 K to 673 K. Single crystalline sheets with thicknesses ≤75 nm down to five layer (3 nm) could be obtained by using a pure CVT process. According to the deposited nanostructures we approve the desired composition, morphology, phase purity and high crystallinity by using several microscopy and spectroscopy techniques. Furthermore, we show micro-RAMAN measurements which hint at a slight increase in phonon energies for nanosheets in comparison to the corresponding bulk phase.show moreshow less

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Metadaten
Author: Martin GrönkeORCiD, Danny Pohflepp, Peer SchmidtORCiD, Martin ValldorORCiD, Steffen Oswald, Daniel WolfORCiD, Qi HaoORCiD, Udo SteinerORCiD, Bernd BüchnerORCiD, Silke HampelORCiD
URL:https://www.sciencedirect.com/science/article/pii/S2352507X18304888?via%3Dihub#!
DOI:https://doi.org/10.1016/j.nanoso.2019.100324
ISSN:2352-507X
Title of the source (English):Nano-Structures & Nano-Objects
Document Type:Scientific journal article peer-reviewed
Language:English
Year of publication:2019
Tag:2D layered compounds; Chemical vapor transport; Crystal growth; Halides
Issue number:19
First Page:1
Last Page:7
Article number:100324
Faculty/Chair:Fakultät 2 Umwelt und Naturwissenschaften / FG Anorganische Chemie
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