Surface-enhanced Raman spectroscopy: a half-century historical perspective.

Surface-enhanced Raman spectroscopy (SERS) has evolved significantly over fifty years into a powerful analytical technique. This review aims to achieve five main goals. (1) Providing a comprehensive history of SERS's discovery, its experimental and theoretical foundations, its connections to advances in nanoscience and plasmonics, and highlighting collective contributions of key pioneers.

Active Plasmonics and Active Chiral Plasmonics through Orientation-Dependent Multipolar Interactions.

While most active plasmonic efforts focus on responsive metamaterials to modulate optical response, we present a simple alternative based on applied orientation control that can likely be implemented for many passive plasmonic materials. Passive plasmonic motifs are simpler to prepare but cannot be altered postfabrication. We show that such systems can be easily manipulated through substrate orientation control to generate both active plasmonic and active chiral plasmonic responses.

Efficient Plasmon-Mediated Energy Funneling to the Surface of Au@Pt Core-Shell Nanocrystals.

The structure and ultrafast photodynamics of ∼8 nm Au@Pt core-shell nanocrystals with ultrathin (<3 atomic layers) Pt-Au alloy shells are investigated to show that they meet the design principles for efficient bimetallic plasmonic photocatalysis. Photoelectron spectra recorded at two different photon energies are used to determine the radial concentration profile of the Pt-Au shell and the electron density near the Fermi energy, which play a key role in plasmon damping and electronic and thermal conductivity. Transient absorption measurements track the flow of energy from the plasmonic core to the electronic manifold of the Pt shell and back to the lattice of the core in the form of heat.

Bias-Dependent Chemical Enhancement and Nonclassical Stark Effect in Tip-Enhanced Raman Spectromicroscopy of CO-Terminated Ag Tips.

Tip-enhanced Raman spectromicroscopy (TERS) with CO-terminated plasmonic tips can probe angstrom-scale features of molecules on surfaces. The development of this technique requires understanding of how chemical environments affect the CO vibrational frequency and TERS intensity. At the scanning tunneling microscope junction of a CO-terminated Ag tip, we show that rather than the classical vibrational Stark effect, the large bias dependence of the CO frequency shift is due to ground-state charge transfer from the Ag tip into the CO π* orbital softening the C-O bond at more positive biases.

Tip-Enhanced Raman Spectromicroscopy on the Angstrom Scale: Bare and CO-Terminated Ag Tips.

The tip is key to the successful execution of tip-enhanced Raman scattering (TERS) measurements in the single molecule limit. We show that nanoscopically smooth silver tips, batch produced through field-directed sputter sharpening, reliably attain TERS with enhancement factors that reach 10, as measured by the Raman spectra of single CO molecules attached to the tip apex. We validate the bare tips by demonstrating spectromicroscopy with submolecular spatial resolution and underscore that TERS is a near-field effect that does not obey simple selection rules.

Tip-Enhanced Raman Spectromicroscopy of Co(II)-Tetraphenylporphyrin on Au(111): Toward the Chemists' Microscope.

Atomically terminated and nanoscopically smooth silver tips effectively focus light on the angstrom scale, allowing tip-enhanced Raman spectromicroscopy (TER-sm) with single molecule sensitivity and submolecular spatial resolution. Through measurements carried out on cobalt-tetraphenylporphyrin (CoTPP) adsorbed on Au(111), we highlight peculiarities of vibrational spectromicroscopy with light confined on the angstrom scale. Field-gradient-driven spectra, orientational fingerprinting, and sculpting of local fields by atomic morphology of the junction are elucidated through measurements that range from 2D arrays at room temperature to single molecule manipulations at 5 K.

Single electron bipolar conductance switch driven by the molecular Aharonov-Bohm effect.

We demonstrate a conductance switch controlled by the spin-vibronic density of an odd electron on a single molecule. The junction current is modulated by the spin-flip bistability of the electron. Functional images are provided as wiring diagrams for control of the switch's frequency, amplitude, polarity, and duty-cycle.

Vibronic motion with joint angstrom-femtosecond resolution observed through Fano progressions recorded within one molecule.

Electroluminescence (EL) in scanning tunneling microscopy (STM), which enables spectroscopy with submolecular spatial resolution, is shown to be due to radiative ionization with vibronic shape resonances that carry Fano line profiles. Since Fano progressions retain phase information, the spectra can be transformed to the time domain to reconstruct the vibronic motion. In effect, measurements within a molecule are accessible with joint space-time resolution at the Å-fs limit.