Relationship between the ionization and oxidation potentials of molecular organic semiconductors |
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| Affiliation: | 1. Department of Electrical Engineering, EQUAD B301, Princeton University, Princeton, NJ 08544, United States;2. Department of Chemistry, University of Southern California, Los Angeles, CA 90089, United States;1. State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Microelectronics and Solid-State Electronics, University of Electronic Science and Technology of China, Chengdu, 610054, PR China;2. College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, PR China;1. Department of Electrical Engineering and Computer Science, University of Michigan, Ann Arbor, MI 48109, USA;2. Department of Physics, University of Michigan, Ann Arbor, MI 48109, USA;3. Department of Chemistry, University of Southern California, Los Angeles, CA 90089, USA;4. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USA;1. School of Chemical Engineering, Sungkyunkwan University, 2066, Seobu-ro, Jangan-gu, Suwon, Gyeonggi-do 16419, Republic of Korea;2. Display Research Center, Samsung Display Co., Samsung-ro, Giheung-gu, Yongin, Gyeonggi-do, Republic of Korea;3. Samsung Advanced Institute of Technology, Samsung Electronics, Suwon, Gyeonggi-do 16678, Republic of Korea;1. Frontiers Science Center for Smart Materials, College of Chemical Engineering, Dalian University of Technology, 2 Linggong Road, Dalian, 116024, China;2. Shandong Laboratory of Yantai Advanced Materials and Green Manufacturing, Yantai Economic and Technological Development Zone, 300 Changjiang Road, Yantai, China;1. Chemistry Group, Middle East Technical University Northern Cyprus Campus (METU NCC), Kalkanl?, Güzelyurt, via Mersin 10, Turkey;2. Sustainable Environment and Energy Systems, Middle East Technical University Northern Cyprus Campus (METU NCC), Kalkanl?, Güzelyurt, via Mersin 10, Turkey |
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| Abstract: | A relationship between the energy of the highest occupied molecular orbital (HOMO) and the oxidation potential of molecular organic semiconductors is presented. Approximating molecules as dipoles consisting of a positively charged ion core surrounded by an electron cloud, the HOMO energy (EHOMO) is calculated as that required to separate these opposite charges in a neutral organic thin film. Furthermore, an analysis of image charge forces on spherical molecules positioned near a conductive plane formed by the electrode in an electrochemical cell is shown to explain the observed linear relationship between EHOMO and the oxidation potential. The EHOMO’s of a number of organic semiconductors commonly employed in thin film electronic devices were determined by ultraviolet photoemission spectroscopy, and compared to the relative oxidation potential (VCV) measured using pulsed cyclic voltammetry, leading to the relationship EHOMO = ?(1.4 ± 0.1) × (qVCV) ? (4.6 ± 0.08) eV, consistent with theoretical predictions. |
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