Charge accumulation at organic semiconductor interfaces due to a permanent dipole moment and its orientational order in bilayer devices

Charge accumulation at the organic heterointerfaces in multilayer organic light-emitting diodes (OLEDs) is an important process for understanding their device operation, efficiency, and degradation properties. Charge accumulation behavior has typically been analyzed in terms of the energy barrier and difference of the charge carrier mobility across heterointerfaces. In this study, we demonstrate that permanent dipole moments and their orientational order also play a significant role in the charge behavior at organic semiconductor interfaces. The charge accumulation properties of bilayer devices composed of polar or nonpolar molecules deposited on a 4,4’-bis[N-(1-naphthyl)-N-phenylamino]-biphenyl layer between the anode and cathode were examined by displacement current measurement and impedance spectroscopy. In addition, Kelvin probe measurements for the corresponding bilayer structures excluding the cathode were performed to analyze the relationship between the potential profile and charge accumulation properties of the bilayer devices. We found that several polar molecules including tris-(8-hydroxyquinolate) aluminum, 1,3,5-tris(1-phenyl-1 H-benzimidazol-2-yl)benzene, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene (OXD-7) are spontaneously ordered in evaporated films, and orientation polarization remains in bilayer devices. Orientation polarization leads to interface charge which determines the least amount of accumulated charge in the device under operation. The estimated interface charge density for these molecules ranged from −2.3 (OXD-7) to −0.5 (BCP) mC/m2. Furthermore, impedance spectroscopy revealed that the presence of a permanent dipole moment can suppress the charge dispersion along the interface probably owing to the microscopic potential fluctuation formed in the vicinity of the interface. These results indicate that the permanent dipole moment and orientation polarization contribute to the efficient charge accumulation at organic heterointerfaces and are important parameters for understanding and controlling the charge carrier dynamics in multilayer OLEDs.