Ultrafast Fluctuations in PM6 Domains of Binary and Ternary Organic Photovoltaic Thin Films Probed with Two-Dimensional White-Light Spectroscopy.

We present two-dimensional white-light spectroscopy (2DWL) measurements of binary and ternary bulk heterojunctions of the polymer donor PM6 mixed with state-of-the-art nonfullerene acceptors Y6 or IT4F. The ternary film has a shorter lifetime and faster spectral diffusion than either of the binary films. 2D line shape analysis of the PM6 ground state bleach with a Kubo model determines that all three films have similar amplitudes of fluctuations (Δ = 0.29 fs-1) in their transition frequencies, but different relaxation times (ranging from 102 to 24 fs). The ternary film exhibits faster dynamics than either of the binary films. The short lifetime of the ternary blend is consistent with increased photoexcitation transfer and the fast frequency fluctuations are consistent with structural dynamics of aliphatic side chains. These results suggest that the femtosecond fluctuations of PM6 are impacted by the choice of the acceptor molecules. We hypothesize that those dynamics are either indicative, or perhaps the initial source, of structural dynamics that ultimately contribute to solar cell operation.

A Proposed Method to Obtain Surface Specificity with Pump-Probe and 2D Spectroscopies.

Surfaces and interfaces are ubiquitous in nature. From cell membranes, to photovoltaic thin films, surfaces have important function in both biological and materials systems. Spectroscopic techniques have been developed to probe systems like these, such as sum frequency generation (SFG) spectroscopies. The advantage of SFG spectroscopy, a second-order spectroscopy, is that it can distinguish between signals produced from molecules in the bulk versus on the surface. We propose a polarization scheme for third-order spectroscopy experiments, such as pump-probe and 2D spectroscopy, to select for surface signals and not bulk signals. This proposed polarization condition uses one pulse perpendicular compared to the other three to isolate cross-peaks arising from molecules with polar and uniaxial (i.e., biaxial) order at a surface, while removing the signal from bulk isotropic molecules. In this work, we focus on two of these cases: XXXY and YYYX, which differ by the sign of the cross-peak they create. We compare this technique to SFG spectroscopy and vibrational circular dichroism to provide insight to the behavior of the cross-peak signal. We propose that these singularly cross-polarized schemes provide odd-ordered spectroscopies the surface-specificity typically associated with even-ordered techniques.

Dual spectral phase and diffraction angle compensation of a broadband AOM 4-f pulse-shaper for ultrafast spectroscopy.

AOM-based pulse shaping as a method has been shown to provide many advantages in the field of ultrafast spectroscopy, in particular for the creation of phase matched pulse pairs for two-dimensional IR and electronic spectroscopy. In this paper we demonstrate the capabilities of a quartz-based AOM pulse-shaper to provide fine control over the phase and spatial dispersion of ultrafast supercontinuum pulses. We show that by using the Bragg condition, we can define a mask function for our AOM such that the angle of diffraction is constant for all frequencies. By summing all the contributions to spectral phase due to normal and anomalous dispersion of our optical components, and taking into account the intrinsic frequency dependent phase as a result of the acoustic sine wave propagating through the AOM, we can determine an optimal mask function that meets the Bragg condition for all frequencies, and generates compressed (∼50 fs) supercontinuum pulses.

Two-Dimensional White-Light Spectroscopy Using Supercontinuum from an All-Normal Dispersion Photonic Crystal Fiber Pumped by a 70 MHz Yb Fiber Oscillator.

We report on a new broadband, ultrafast two-dimensional white-light (2DWL) spectrometer that utilizes a supercontinuum pump and a supercontinuum probe generated with a ytterbium fiber oscillator and an all-normal dispersion photonic crystal fiber (ANDi PCF). We demonstrate compression of the supercontinuum to sub-20 fs and the ability to collect high quality 2D spectra on films of single-walled carbon nanotubes. Two spectrometer designs are investigated. Supercontinuum from ANDi PCF provides a means to generate broadband pulse sequences for multidimensional spectroscopy without the need for an optical parametric amplifier.