Colloidal Nanoantennas for Hyperspectral Chemical Mapping

Tip-enhanced Raman spectroscopy enables access to chemical information with nanoscale spatial resolution and single-molecule sensitivities by utilizing optical probes that are capable of confining light to subwavelength dimensions. Because the probes themselves possess nanoscale features, they are notoriously difficult to fabricate, and more critically, can result in poor reproducibility. Here, we demonstrate high-performance, predictable, and readily tunable nanospectroscopy probes that are fabricated by self-assembly. Shaped metal nanoparticles are organized into dense layers and deposited onto scanning probe tips. When coupled to a metal surface, these probes behave like nanoantenna by supporting a strong optical resonance, producing dramatic Raman field enhancements in the range of 10(8)-10(9) with sub-50 nm spatial resolution. In contrast to other nanospectroscopy probes, our colloidal probes can be fabricated in a scalable fashion with a batch-to-batch reproducibility of ∼80% and serve as an important demonstration of bottom-up engineering.