Molecular emission near metal interfaces: the polaritonic regime

TL;DR

This paper theoretically investigates the superradiant emission of bright plexcitons formed by strong coupling of molecular excitons with surface plasmons, revealing significant photoluminescence enhancements and new design principles for molecular photophysics.

Contribution

It generalizes molecular emission near metal interfaces to collective states, providing novel insights into polaritonic control of molecular photophysical properties.

Findings

Bright plexcitons exhibit large photoluminescence enhancements.

Superradiant emission is prominent in the upper polaritonic branch.

Provides design principles for manipulating molecular emission using polaritons.

Abstract

The strong coupling of a dense layer of molecular excitons with surface-plasmon modes in a metal gives rise to polaritons (hybrid light-matter states) called plexcitons. Surface plasmons cannot directly emit into (or be excited by) free-space photons due to the fact that energy and momentum conservation cannot be simultaneously satisfied in photoluminescence. Most plexcitons are also formally non-emissive, even though they can radiate via molecules upon localization due to disorder and decoherence. However, a fraction of them are bright even in the presence of such deleterious processes. In this letter, we theoretically discuss the superradiant emission properties of these bright plexcitons, which belong to the upper energy branch and reveal huge photoluminescence enhancements compared to bare excitons. Our study generalizes the well-known problem of molecular emission next to a metal interface to collective molecular states and provides new design principles for the control of photophysical properties of molecular aggregates using polaritonic strategies.