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Surface functionalization of low-dimensional nanomaterials offers a means to tailor their optoelectronic and chemical characteristics. However, functionalization reactions are sensitive to the inherent surface features of nanomaterials, such as defects, grain boundaries, and edges. Conventional optical characterization methods, such as Raman spectroscopy, have limited sensitivity and spatial resolution and, therefore, struggle to visualize reaction sites and chemical species. Here, we demonstrate the capability of spatially and chemically sensitive tip-enhanced Raman spectroscopy imaging to map the distribution of molecules in covalently functionalized graphene. Hyperspectral vertex component analysis and density functional theory are necessary to interpret the nature of binding sites and extract information from the spatially and spectrally heterogeneous datasets. Our results clarify the origin of heterogeneous surface functionalization, resolving preferential binding at edges and defects. This work demonstrates the potential of nanospectroscopic tools combined with unsupervised learning to characterize complex, partially ordered optoelectronic nanomaterials.
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Uncovering topographically hidden features in 2D MoSe2 with correlated potential and optical nanoprobes
Abstract Developing characterization strategies to better understand nanoscale features in two-dimensional nanomaterials is of crucial importance, as the properties of these materials are many times driven by nanoscale and microscale chemical and structural modifications within the material. For the case of large area monolayer MoSe2flakes, kelvin probe force microscopy coupled with tip-enhanced photoluminescence was utilized to evaluate such features including internal grain boundaries, edge effects, bilayer contributions, and effects of oxidation/aging, many of which are invisible to topographical mapping. A reduction in surface potential due ton-type behavior was observed at the edge of the flakes as well as near grain boundaries. Potential phase mapping, which corresponds to the local dielectric constant, depicted local biexciton and trion states in optically-active regions of interest such as grain boundaries. Finally, nanoscale surface potential and photoluminescence mapping was performed at several stages of oxidation, revealing that various oxidative states can be evaluated during the aging process. Importantly, all of the characterization performed in this study was non-destructive and rapid, crucial for quality evaluation of an exciting class of two-dimensional nanomaterials.
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- Award ID(s):
- 1905853
- PAR ID:
- 10205070
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- npj 2D Materials and Applications
- Volume:
- 4
- Issue:
- 1
- ISSN:
- 2397-7132
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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