A nanophotonic interferometer.

The transmission of light through sub-wavelength apertures (zero-mode waveguides, ZMW) in metal films is well-explored. It introduces both an amplitude modulation as well as a phase shift to the oscillating electromagnetic field. We propose a nanophotonic interferometer by bringing two ZMW (∼100 nm diameter) in proximity and monitoring the distribution of transmitted light in the back-focal plane of collecting microscope objective (1.3 N.A.). We demonstrate that both an asymmetry induced by the binding of a quantum dot in one of the two ZMW, as well as an asymmetry in ZMW diameter yield qualitatively similar transmission patterns. We find that the complex pattern can be quantified through a scalar measure of asymmetry along the symmetry axis of the aperture pair. In a combined experimental and computational exploration of detectors with differing ZMW diameters, we find that the scalar asymmetry is a monotonous function of the diameter difference of the two apertures, and that the scalar asymmetry measure is higher if the sample is slightly displaced from the focal plane of the collecting microscope objective. An optimization of the detector geometry determined that the maximum response is achieved at an aperture separation that is comparable to the wavelength on the exit side of the sensor. For small separations of apertures, on the order of a quarter of the wavelength and less, the signal is strongly polarization dependent, while for larger separations, on the order of the wavelength or larger, the signal becomes essentially polarization-independent.

Relating reorganization energies, exciton diffusion length and non-radiative recombination to the room temperature UV-vis absorption spectra of NF-SMA.

Understanding excited-state reorganization energies, exciton diffusion lengths and non-radiative (NR) recombination, and the overall optoelectronic responses of nonfullerene small molecule acceptors (NF-SMAs) is important in order to rationally design new materials with controlled properties. While the effects of structural modifications on the optical gaps and electron affinities of NF-SMAs have been studied extensively, analyses of their absorption spectra that carefully characterize electronic and vibrational contributions that allow comparisons of reorganization energies and their implications for exciton diffusion lengths and NR recombination have yet to be reported. Here, we study the room temperature absorption spectra of three structural classes of NF-SMAs in dilute solutions through multiparameter Franck Condon (MFC) analyses and density functional theory (DFT) calculations. We show that the absorption spectra of these NF-SMAs can be categorized based on molecular structure-spectra correlation. The absorption spectra of curved, Y6-like structures can be described using an MFC model with two electronic transitions and two effective vibrational modes. The results of MFC/DFT analyses reveal that Y6 exhibits the smallest intra-molecular reorganization energy among the materials studied. Linear ITIC-like molecular structures reveal larger reorganization energies and reduced conformational uniformity compared to Y6. Meanwhile structures such as IDTBR and IEICO, which have an extra π-conjugated moiety between the donor and acceptor moieties, have large excited-state reorganization energies and low degrees of conformational uniformity. Since the intra-molecular reorganization energy is correlated with exciton diffusion length and nonradiative voltage losses (ΔVnr), our results highlight the power of RT absorption spectroscopy and DFT calculations as simple tools to designing improved OSCs materials with small reorganization energies, small ΔVnr, large exciton diffusion length and low energetic disorder (due to a strongly dominant conformation).