Nanofabrication of plasmon-tunable nanoantennas for tip-enhanced Raman spectroscopy
Bruno Oliveira, Bráulio S. Archanjo, Rogério Valaski, Carlos A. Achete, Luiz Gustavo Cançado, Ado Jório, Thiago L. Vasconcelos
Abstract
Plasmon-tunable tip pyramids (PTTPs) are reproducible and efficient nanoantennas for tip-enhanced Raman spectroscopy (TERS). Their fabrication method is based on template stripping of a segmented gold pyramid with a size-adjustable nanopyramid end, which is capable of supporting monopole localized surface plasmon resonance (LSPR) modes leading to high spectral enhancement when its resonance energy is matched with the excitation laser energy. Here, we describe in detail the PTTP fabrication method and report a statistical analysis based on 530 PTTPs' and 185 ordinary gold micropyramids' templates. Our results indicate that the PTTP method generates probes with an apex diameter smaller than 30 nm on 92.4% of the batch, which is a parameter directly related to the achievable TERS spatial resolution. Moreover, the PTTPs' nanopyramid edge size L, a critical parameter for LSPR spectral tuning, shows variability typically smaller than 12.5%. The PTTP's performance was tested in TERS experiments performed on graphene, and the results show a spectral enhancement of up to 72-fold, which is at least one order of magnitude higher than that typically achieved with gold micropyramids. Imaging resolution is in the order of 20 nm.