Substitution effects on the photoinduced excited state dynamics of perylenemonoimides in solution and thin films.

Perylene monoimide (PMI) derivatives are attracting significant attention due to their strong absorption in the visible range, thermal stability, and synthetic accessibility. These properties make them promising for application in various areas such as optoelectronic devices, photosensitizers, etc. In this work, the photophysical properties and excited state dynamics of four different PMI derivatives (PMIB, BrPMITB, PMITB, and APITB) were studied in solution and thin films utilizing steady-state and time-resolved spectroscopic techniques. Among the four PMI derivatives, APITB is designed as a donor-acceptor dyad, with thianthrene as a donor and PMI as an acceptor. The activation of the triplet state through the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process in THF was observed upon substitution with the thianthrene group at the peri position of the PMI moiety. The SOCT-ISC process facilitates triplet formation in the APITB dyad within 423 ps. Meanwhile, other PMI derivatives showed fluorescence within the femtosecond timescale in THF. The PMI derivatives in thin films displayed different photo physical properties to those in THF. This discrepancy arises due to the effective intermolecular coupling between the PMI derivatives in thin films.

Probing the excited state dynamics in perinone molecules for photovoltaic applications using transient absorption spectroscopy.

Nonfullerene polyaromatic molecules such as perinone are emerging as alternatives to fullerene derivatives due to their low manufacturing cost, ease of functionalization, and processing to improve the efficiency of optoelectronic devices. In this paper, we have used ultrafast transient absorption (TA) spectroscopy to probe the excited state dynamics in cis and trans perinone molecules. We have performed TA measurements in solution as well as thin films to provide a comprehensive understanding of excited-state processes occurring in cis and trans perinone molecules. Our results reveal the triplet state formation in perinone thin films through intersystem crossing and provide an in-depth understanding of the relaxation pathways of perinone molecules, which will be beneficial for designing and optimizing the device efficiencies of perinone based photovoltaic devices.

Development of electronic sum frequency generation spectrophotometer to assess the buried interfaces.

The interfacial region between two bulk media in organic semiconductor based devices, such as organic field-effect transistors (OFETs), organic light-emitting diodes, and organic photovoltaics, refers to the region where two different materials such as an organic material and an electrode come in contact with each other. Although the interfacial region contains a significantly smaller fraction of molecules compared to the bulk, it is the primary site where many photoinduced excited state processes occur, such as charge transfer, charge recombination, separation, energy transfer processes, etc. All such photoinduced processes have a dependence on molecular orientation and density of states at the interfaces, therefore having an understanding of the interfacial region is essential. However, conventional spectroscopic techniques, such as surface-enhanced Raman scattering, x-ray photoelectron spectroscopy, atomic force microscopy, etc., face limitations in probing the orientation and density of states of interfacial molecules. Therefore, there is a need for noninvasive techniques capable of efficiently investigating the interfaces. The electronic sum frequency generation (ESFG) technique offers an interface selectivity based on the principle that the second-order nonlinear susceptibility tensor, within the electric dipole approximation, is zero in the isotropic bulk but nonzero at interfaces. This selectivity makes ESFG a promising spectroscopy tool to probe the molecular orientation and density of states at the buried interface. For beginners interested in employing ESFG to study the density of states at the interface, a detailed description of the experimental setup is provided here.

Theoretical study of electronic sum frequency generation spectroscopy to assess the buried interfaces.

This article provides a comprehensive theoretical background of electronic sum frequency generation (ESFG), a second-order nonlinear spectroscopy technique. ESFG is utilized to investigate both exposed and buried interfaces, which are challenging to study using conventional spectroscopic methods. By overlapping two incident beams at the interface, ESFG generates a beam at the sum of their frequencies, allowing for the extraction of valuable interfacial molecular information such as molecular orientation and density of states present at interfaces. The unique surface selectivity of ESFG arises from the absence of inversion symmetry at the interfaces. However, detecting weak signals from interfaces requires the ultrafast lasers to generate a sufficiently strong signal. By understanding the theoretical foundations of ESFG presented in this article, readers can gain a solid grasp of the basics of ESFG spectroscopy.