Gate-tunable electroluminescence in Aviram–Ratner-type molecules: Kinetic description

• Published in: The Journal of chemical physics 2020-08, Vol.153 (8), p.084105-084105
• Main Authors: Petrov, Elmar G., Gorbach, Victor V., Ragulya, Andrey V., Lyubchik, Andrey, Lyubchik, Svetlana
• Format: Article
• Language: English
• Subjects: Chemical bonds; Coupling (molecular); Electric potential; Electroluminescence; Electron transitions; Molecular orbitals; Occupancy; Polarity; Single-electron transitions; Voltage
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0018574

A theoretical study of the mechanisms of electroluminescence (EL) generation in photoactive molecules with donor and acceptor centers linked by saturated σ-bonds (molecules of the Aviram–Ratner-type) is presented. The approach is based on the kinetics of single-electron transitions between many-body molecular states. This study shows that the EL polarity arises due to asymmetric coupling of molecular orbitals of the photochromic part of the molecule to the electrodes. The gate voltage controls the power of the EL through the occupancy of the excited singlet state. The shifting of the orbital energies forms a resonant or a non-resonant path for the transmission of electrons through the molecule. The action of the gate voltage is reflected in specific critical voltages. An analytical dependence of the critical voltages on the energies of molecular states involved in the formation of EL, as well as on the gate voltage, was derived for both positive and negative polarities. Conditions under which the gate voltage lowers the absolute value of the bias voltage that is responsible for the activation of the resonance mechanism of EL formation were also established. This is an important factor in control of EL in molecular junctions.