High-throughput large-area plastic nanoelectronics

Large-area electronics (LAE) manufacturing has been a key focus of both academic and industrial research, especially within the last decade. The growing interest is born out of the possibility of adding attractive properties (flexibility, light weight or minimal thickness) at low cost to well-established technologies, such as photovoltaics, displays, sensors or enabling the realisation of emerging technologies such as wearable devices and the Internet of Things. As such there has been great progress in the development of materials specifically designed to be employed in solution processed (plastic) electronics, including organic, transparent metal oxide and nanoscale semiconductors, as well as progress in the deposition methods of these materials using low-cost high-throughput printing techniques, such as gravure printing, inkjet printing, and roll-to-roll vacuum deposition. Meanwhile, industry innovation driven by Moore’s law has pushed conventional silicon-based electronic components to the nanoscale. The processes developed for LAE must strive to reach these dimensions. Given that the complex and expensive patterning techniques employed by the semiconductor industry so far are not compatible with LAE, there is clearly a need to develop large-area high throughput nanofabrication techniques. This thesis presents progress in adhesion lithography (a-Lith), a nanogap electrode fabrication process that can be applied over large areas on arbitrary substrates. A-Lith is a self-alignment process based on the alteration of surface energies of a starting metal electrode which allows the removal of any overlap of a secondary metal electrode. Importantly, it is an inexpensive, scalable and high throughput technique, and, especially if combined with low temperature deposition of the active material, it is fundamentally compatible with large-area fabrication of nanoscale electronic devices on flexible (plastic) substrates. Herein, I present routes towards process optimisation with a focus on gap size reduction and yield maximisation. Asymmetric gaps with sizes below 10 nm and yields of > 90 % for hundreds of electrode pairs generated on a single substrate are demonstrated. These large width electrode nanogaps represent the highest aspect ratio nanogaps (up to 108) fabricated to date. As a next step, arrays of Schottky nanodiodes are fabricated by deposition of a suitable semiconductor from solution into the nanogap structures. Of principal interest is the wide bandgap transparent semiconductor, zinc oxide (ZnO). Lateral ZnO Schottky diodes show outstanding characteristics, with on-off ratios of up to 106 and forward current values up to 10 mA for obtained upon combining a-Lith with low-temperature solution processing. These unique devices are further investigated for application in rectifier circuits, and in particular for potential use in radio frequency identification (RFID) tag technology. The ZnO diodes are found to surpass the 13.56 MHz frequency bernchmark used in commercial applications and approach the ultra-high frequency (UHF) band (hundreds of megahertz), outperforming current state of the art printed diodes. Solution processed fullerene (C60) is also shown to approach the UHF band in this co-planar device configuration, highlighting the viability of a-Lith for enabling large-area flexible radio frequency nanoelectronics. Finally, resistive switching memory device arrays based on a-Lith patterned nanogap aluminium symmetric electrodes are demonstrated for the first time. These devices are based either on empty aluminium nanogap electrodes, or with the gap filled with a solution-processed semiconductor, the latter being ZnO, the semiconducting polymer poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) or carbon nanotube/polyfluorene blends. The switching mechanism, retention time and switching speed are investigated and compared with published data. The fabrication of arrays of these devices illustrates the potential of a-Lith as a simple technique for the realisation of large-area high-density memory applications.Open Acces