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.

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