A series of optical and electron microscopies are utilized in concert to unravel the properties of corrugated metallic tips. While the overall microscopic shapes of the tips dictate their optical resonances and plasmonic field enhancement factors, nanometric structural details govern their tip-enhanced Raman (TER) spectra and images. Using 4thiobenzonitrile (TBN) as a molecular reporter, spatially resolved TER spectra reveal that optical rectification and molecular charging are among the prominent observables in the tip− tip TER geometry. We show the spurious appearance of anions is driven by highly localized resonances that appear as a result of surface corrugation and their manifestation throughout the course of TER nanospectroscopy complicates spectral assignments. Overall, nanoscale spatial variations in the TERS spectra suggest that the tip−tip geometry sustains junction plasmons that appear very different from what may be expected from the hybridization of the bulk tip resonances.

Classical versus quantum plasmons are responsible for the recorded signals in non-contact-mode versus contact-mode tip-enhanced Raman spectroscopy (TERS) and lead to distinct observables. Under otherwise identical experimental conditions, we illustrate the concept through tapping- and contact-mode TERS mapping of chemically functionalized silver nanocubes. Whereas molecular charging, chemical transformations, and optical rectification are prominent observables in contact-mode TERS, the same effects are suppressed using tapping-mode feedback. In effect, this work demonstrates that nanoscale physical and chemical processes can be accessed and/or suppressed on demand in the TERS geometry. The advantages of tapping-mode TERS are otherwise highlighted with the latter in mind.

We record nanoscale chemical images of thiobenzonitrile (TBN)-functionalized plasmonic gold nanocubes via tip-enhanced Raman spectroscopy (TERS). The spatially averaged optical response is dominated by conventional (dipolar) TERS scattering from TBN but also contains weaker spectral signatures in the 1225–1500 cm–1 region. The weak optical signatures dominate several of the recorded single-pixel TERS spectra. We can uniquely assign these Raman-forbidden transitions to multipolar Raman scattering, which implicates spatially varying enhanced electric field gradients at plasmonic tip–sample nanojunctions. Specifically, we can assign observations of tip-enhanced electric dipole–magnetic dipole as well as electric dipole–electric quadrupole driven transitions. Multipolar Raman scattering and local optical field gradients both need to be understood and accounted for in the interpretation of TERS spectral images, particularly in ongoing quests aimed at chemical reaction mapping via TERS.

We revisit the reductive coupling of p-nitrothiophenol (NTP) to form dimercaptoazobenzene (DMAB), herein monitored through gap-mode tip-enhanced Raman spectroscopy (TERS) and nanoimaging. We employ a plasmonic Au probe (100 nm diameter at its apex) illuminated with a 633 nm laser source (50 μW/μm2 at the sample position) to image an NTP-coated faceted silver nanoparticle (∼70 nm diameter). A detailed analysis of the recorded spectra reveals that anionic NTP species contribute to the recorded spectral images, in addition to the more thoroughly described DMAB product. Notably, the signatures of the anions are more pronounced than those of the DMAB product under our present experimental conditions. Our results thus demonstrate that anions and their spectral signatures must be considered in the analysis of plasmon-enhanced optical spectra and images.

Wigner function modeling of quantum well semiconductor lasers using classical electromagnetic field coupling J. Appl. Phys. 93, 9562 (2003); 10.1063/1.1574180Additional Coulomb blockade and negative differential conductance in closed two-dimensional tunnel junction arrays We propose a model, by taking advantage of quantum interference in a semiconductor quantum-well structure, for two-color lasing without population inversion. In the suggested three-well system, transitions of the lowest three excited states, being coupled to a common continuum by tunneling, to the ground state have been studied. Our results show that the emission spectrum can be arranged in accordance with the initial conditions of the excited states. With the emission peaks located in the vicinities of the absorption zeros resulting from destructive interferences, the nonreciprocal emission-absorption spectra provide a choice of inversionless lasing at two frequencies.