Atomic Point Contact Raman Spectroscopy of a Si(111)-7 × 7 Surface

[Image: see text] Tip-enhanced Raman scattering (TERS) has recently demonstrated the exceptional sensitivity to observe vibrational structures on the atomic scale. However, it strongly relies on electromagnetic enhancement in plasmonic nanogaps. Here, we demonstrate that atomic point contact (APC) formation between a plasmonic tip and the surface of a bulk Si sample can lead to a dramatic enhancement of Raman scattering and consequently the phonons of the reconstructed Si(111)-7 × 7 surface can be detected. Furthermore, we demonstrate the chemical sensitivity of APC-TERS by probing local vibrations resulting from Si–O bonds on the partially oxidized Si(111)-7 × 7 surface. This approach will expand the applicability of ultrasensitive TERS, exceeding the previous measurement strategies that exploit intense gap-mode plasmons, typically requiring a plasmonic substrate.