TY - JOUR
T1 - Tuning the Fermi Level of Graphene by Two-Dimensional Metals for Raman Detection of Molecules
AU - Zhang, Na
AU - Zhang, Kunyan
AU - Zou, Min
AU - Maniyara, Rinu Abraham
AU - Bowen, Timothy Andrew
AU - Schrecengost, Jonathon Ray
AU - Jain, Arpit
AU - Zhou, Da
AU - Dong, Chengye
AU - Yu, Zhuohang
AU - Liu, He
AU - Giebink, Noel C.
AU - Robinson, Joshua A.
AU - Hu, Wei
AU - Huang, Shengxi
AU - Terrones, Mauricio
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/3/26
Y1 - 2024/3/26
N2 - Graphene-enhanced Raman scattering (GERS) offers great opportunities to achieve optical sensing with a high uniformity and superior molecular selectivity. The GERS mechanism relies on charge transfer between molecules and graphene, which is difficult to manipulate by varying the band alignment between graphene and the molecules. In this work, we synthesized a few atomic layers of metal termed two-dimensional (2D) metal to precisely and deterministically modify the graphene Fermi level. Using copper phthalocyanine (CuPc) as a representative molecule, we demonstrated that tuning the Fermi level can significantly improve the signal enhancement and molecular selectivity of GERS. Specifically, aligning the Fermi level of graphene closer to the highest occupied molecular orbital (HOMO) of CuPc results in a more pronounced Raman enhancement. Density functional theory (DFT) calculations of the charge density distribution reproduce the enhanced charge transfer between CuPc molecules and graphene with a modulated Fermi level. Extending our investigation to other molecules such as rhodamine 6G, rhodamine B, crystal violet, and F16CuPc, we showed that 2D metals enabled Fermi level tuning, thus improving GERS detection for molecules and contributing to an enhanced molecular selectivity. This underscores the potential of utilizing 2D metals for the precise control and optimization of GERS applications, which will benefit the development of highly sensitive, specific, and reliable sensors.
AB - Graphene-enhanced Raman scattering (GERS) offers great opportunities to achieve optical sensing with a high uniformity and superior molecular selectivity. The GERS mechanism relies on charge transfer between molecules and graphene, which is difficult to manipulate by varying the band alignment between graphene and the molecules. In this work, we synthesized a few atomic layers of metal termed two-dimensional (2D) metal to precisely and deterministically modify the graphene Fermi level. Using copper phthalocyanine (CuPc) as a representative molecule, we demonstrated that tuning the Fermi level can significantly improve the signal enhancement and molecular selectivity of GERS. Specifically, aligning the Fermi level of graphene closer to the highest occupied molecular orbital (HOMO) of CuPc results in a more pronounced Raman enhancement. Density functional theory (DFT) calculations of the charge density distribution reproduce the enhanced charge transfer between CuPc molecules and graphene with a modulated Fermi level. Extending our investigation to other molecules such as rhodamine 6G, rhodamine B, crystal violet, and F16CuPc, we showed that 2D metals enabled Fermi level tuning, thus improving GERS detection for molecules and contributing to an enhanced molecular selectivity. This underscores the potential of utilizing 2D metals for the precise control and optimization of GERS applications, which will benefit the development of highly sensitive, specific, and reliable sensors.
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U2 - 10.1021/acsnano.3c12152
DO - 10.1021/acsnano.3c12152
M3 - Article
C2 - 38497598
AN - SCOPUS:85188049188
SN - 1936-0851
VL - 18
SP - 8876
EP - 8884
JO - ACS nano
JF - ACS nano
IS - 12
ER -