Calculation of Dielectric Response in Molecular Solids for High Capacitance Organic Dielectrics

The dielectric response of a material is critically important in numerous scientific processes spanning the fields of biology, chemistry, materials science, and physics. While important across these fundamental disciplines, it remains difficult to determine theoretically the dielectric environment of a system. With recent advances in nanotechnology, biochemistry, and molecular electronics, it has become necessary to determine the dielectric response in molecular systems that are difficult to measure experimentally, such as nanoscale interfaces, highly disordered biological environments, or molecular materials that are difficult to synthesize. In these scenarios it is highly advantageous to determine the dielectric response through efficient and accurate calculations.;A good example of where a theoretical prediction of dielectric response is critical is in the development of high capacitance molecular dielectrics. Molecular dielectrics offer the promise of cheap, flexible, and mass producible electronic devices when used in conjunction with organic semiconducting materials to form Organic Field Effect Transistors (OFETs). To date, molecular dielectrics suffer from poor dielectric properties resulting in low capacitances. A low capacitance dielectric material requires a much larger power source to operate the device in OFETs, leading to modest device performance. Development of better performing dielectric materials has been hindered due to the time it takes to synthesize and fabricate new molecular materials. An accurate and efficient theoretical technique could drastically decrease this time by screening potential dielectric materials and providing design rules for future molecular dielectrics.;Here in, the methodology used to calculate dielectric properties of molecular materials is described. The validity of the technique is demonstrated on model systems, capturing the frequency dependence of the dielectric response and achieving quantitative accuracy compared with experiment. This method is then used to help design new high-capacitance molecular dielectrics by determining what materials and chemical properties are important in maximizing dielectric response in Self-Assembled Monolayers (SAMs). Highly (hyper)polarizable Donor-Bridge-Acceptor (DBA) molecular materials are shown to have remarkable dielectric responses. Lastly, the interplay between charge conduction and dielectric constant is examined and it is demonstrated that high dielectric constant materials with low conductance are achievable through molecular design. This technique is a powerful tool for understanding and designing molecular dielectric systems, whose properties are fundamental in many scientific pursuits.