Interface Engineering To Control Magnetic Field Effects of Organic-Based Devices by Using a Molecular Self-Assembled Monolayer

Organic semiconductors hold immense promise for the development of a wide range of innovative devices with their excellent electronic and manufacturing characteristics. Of particular interest are nonmagnetic organic semiconductors that show unusual magnetic field effects (MFEs) at small subtesla field strength that can result in substantial changes in their optoelectronic and electronic properties. These unique phenomena provide a tremendous opportunity to significantly impact the functionality of organic-based devices and may enable disruptive electronic and spintronic technologies. Here, we present an approach to vary the MFEs on the electrical resistance of organic-based systems in a simple yet reliable fashion. We experimentally modify the interfacial characteristics by adding a self-assembled monolayer between the metal electrode and the organic semiconductor, thus enabling the tuning of competing MFE mechanisms coexisting in organic semiconductors. This approach offers a robust method for tuning the magnitude and sign of magneto­resistance in organic semiconductors without compromising the ease of processing

Direct Observation of Correlated Triplet Pair Dynamics during Singlet Fission Using Ultrafast Mid-IR Spectroscopy

Singlet fission is an exciton multiplication mechanism in organic materials whereby high energy singlet excitons can be converted into two triplet excitons with near unity quantum yields. As new singlet fission sensitizers are developed with properties tailored to specific applications, there is an increasing need for design rules to understand how the molecular structure and crystal packing arrangements influence the rate and yield with which spin-correlated intermediates known as correlated triplet pairs can be successfully separateda prerequisite for harvesting the multiplied triplets. Toward this end, we identify new electronic transitions in the mid-infrared spectral range that are distinct for both initially excited singlet states and correlated triplet pair intermediate states using ultrafast mid-infrared transient absorption spectroscopy of crystalline films of 6,13-bis­(triisopropylsilylethynyl) pentacene (TIPS-Pn). We show that the dissociation dynamics of the intermediates can be measured through the time evolution of the mid-infrared transitions. Combining the mid-infrared with visible transient absorption and photoluminescence methods, we track the dynamics of the relevant electronic states through their unique electronic signatures and find that complete dissociation of the intermediate states to form independent triplet excitons occurs on time scales ranging from 100 ps to 1 ns. Our findings reveal that relaxation processes competing with triplet harvesting or charge transfer may need to be controlled on time scales that are orders of magnitude longer than previously believed even in systems like TIPS-Pn where the primary singlet fission events occur on the sub-picosecond time scale