Dual-Wavelength Control of Charge Accumulation in Rubrene Microcrystals with Anisotropic Conductivity

Previously, a novel type of rubrene microcrystals was reported, forming two distinct sectors-diamond- and triangular-shaped-that exhibit pronounced contrasts in photoluminescence (PL) spectra and exciton dynamics. In the present work, their internal electronic structure is investigated using time-of-flight photoemission electron spectroscopy (TOF-PES), revealing that the two sector's different charging characteristics arise from anisotropic conductivities. Upon photoemission via a one-photon photoemission (1PPE) process excited by 6.2 eV (200 nm) photons, the diamond-shaped sectors accumulate significant charge, whereas the triangular sectors remain essentially uncharged. The charge accumulation in the diamond sectors can be neutralized by additional sub-threshold illumination, which generates charge carriers through internal photoeffect. The dynamics and energetics of the observed band shifting is described quantitatively by a model combining surface capacitance and drift-diffusion. These crystalline systems enable the creation of built-in charge landscapes that can be manipulated both spatially and temporally.