TY - JOUR

T1 - Resonant Raman scattering on graphene: SERS and gap-mode TERS

AU - Kurus, N N

AU - Kalinin, V

AU - Nebogatikova, N A

AU - Milekhin, I A

AU - Antonova, I V

AU - Rodyakina, E E

AU - Milekhin, A G

AU - Latyshev, A V

AU - Zahn, D R T

N1 - The reported study was funded by RFBR according to the research project no. 20-52-04009. This journal is © The Royal Society of Chemistry.

PY - 2024/1/23

Y1 - 2024/1/23

N2 - Nanoscale deformations and corrugations occur in graphene-like two-dimensional materials during their incorporation into hybrid structures and real devices, such as sensors based on surface-enhanced Raman scattering (SERS-based sensors). The structural features mentioned above are known to affect the electronic properties of graphene, thus highly sensitive and high-resolution techniques are required to reveal and characterize arising local defects, mechanical deformations, and phase transformations. In this study, we demonstrate that gap-mode tip-enhanced Raman Scattering (gm-TERS), which offers the benefits of structural and chemical analytical methods, allows variations in the structure and mechanical state of a two-dimensional material to be probed with nanoscale spatial resolution. In this work, we demonstrate locally enhanced gm-TERS on a monolayer graphene film placed on a plasmonic substrate with specific diameter gold nanodisks. SERS measurements are employed to determine the optimal disk diameter and excitation wavelength for further realization of gm-TERS. A significant local plasmonic enhancement of the main vibrational modes in graphene by a factor of 100 and a high spatial resolution of 10 nm are achieved in the gm-TERS experiment, making gm-TERS chemical mapping possible. By analyzing the gm-TERS spectra of the graphene film in the local area of a nanodisk, the local tensile mechanical strain in graphene was detected, resulting in a split of the G mode into two components, G+ and G-. Using the frequency split in the positions of G+ and G- modes in the TERS spectra, the stress was estimated to be up to 1.5%. The results demonstrate that gap-mode TERS mapping allows rapid and precise characterization of local structural defects in two-dimensional materials on the nanoscale.

AB - Nanoscale deformations and corrugations occur in graphene-like two-dimensional materials during their incorporation into hybrid structures and real devices, such as sensors based on surface-enhanced Raman scattering (SERS-based sensors). The structural features mentioned above are known to affect the electronic properties of graphene, thus highly sensitive and high-resolution techniques are required to reveal and characterize arising local defects, mechanical deformations, and phase transformations. In this study, we demonstrate that gap-mode tip-enhanced Raman Scattering (gm-TERS), which offers the benefits of structural and chemical analytical methods, allows variations in the structure and mechanical state of a two-dimensional material to be probed with nanoscale spatial resolution. In this work, we demonstrate locally enhanced gm-TERS on a monolayer graphene film placed on a plasmonic substrate with specific diameter gold nanodisks. SERS measurements are employed to determine the optimal disk diameter and excitation wavelength for further realization of gm-TERS. A significant local plasmonic enhancement of the main vibrational modes in graphene by a factor of 100 and a high spatial resolution of 10 nm are achieved in the gm-TERS experiment, making gm-TERS chemical mapping possible. By analyzing the gm-TERS spectra of the graphene film in the local area of a nanodisk, the local tensile mechanical strain in graphene was detected, resulting in a split of the G mode into two components, G+ and G-. Using the frequency split in the positions of G+ and G- modes in the TERS spectra, the stress was estimated to be up to 1.5%. The results demonstrate that gap-mode TERS mapping allows rapid and precise characterization of local structural defects in two-dimensional materials on the nanoscale.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85184259469&origin=inward&txGid=0c17fc11e4186dc465f9836fabbd8939

UR - https://www.mendeley.com/catalogue/47bb5893-07ca-347b-8e81-5f4033a5c060/

U2 - 10.1039/d3ra07018b

DO - 10.1039/d3ra07018b

M3 - Article

C2 - 38268550

VL - 14

SP - 3667

EP - 3674

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 6

ER -