MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti 4 N 3 and Ti 2 N are the only nitride MXenes reported so far. Here by ammoniation of Mo 2 CT x and V 2 CT x MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures of the resulting Mo 2 N and V 2 N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo 2 N retains the MXene structure and V 2 C transforms to a mixed layered structure of trigonal V 2 N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo 2 N and V 2 N are three and one order of magnitude larger than those of the Mo 2 CT x and V 2 CT x precursors, respectively. This study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis. 
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                            Synthesis of layered vs planar Mo 2 C: role of Mo diffusion
                        
                    
    
            Abstract Chemical vapor deposition growth of metal carbides is of great interest as this method provides large area growth of MXenes. This growth is mainly done using a melted diffusion based process; however, different morphologies in growth process is not well understood. In this work, we report deterministic synthesis of layered (non-uniform c -axis growth) and planar (uniform c -axis growth) of molybdenum carbide (Mo 2 C) using a diffusion-mediated growth. Mo-diffusion limited growth mechanism is proposed where the competition between Mo and C adatoms determines the morphology of grown crystals. Difference in thickness of catalyst at the edge and center lead to enhanced Mo diffusion which plays a vital role in determining the structure of Mo 2 C. The layered structures exhibit an expansion in the lattice confirmed by the presence of strain. Density functional theory shows consistent presence of strain which is dependent upon Mo diffusion during growth. This work demonstrates the importance of precise control of diffusion through the catalyst in determining the structure of Mo 2 C and contributes to broader understanding of metal diffusion in growth of MXenes. 
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                            - Award ID(s):
- 1929356
- PAR ID:
- 10338518
- Date Published:
- Journal Name:
- 2D Materials
- Volume:
- 9
- Issue:
- 1
- ISSN:
- 2053-1583
- Page Range / eLocation ID:
- 015039
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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