title: Dynamic Exchange During Triplet Transport in Nanocrystalline TIPS-Pentacene Films.
abstract: The multiplication of excitons in organic semiconductors via singlet fission offers the potential for photovoltaic cells that exceed the Shockley-Quiesser limit for single-junction devices. To fully utilize the potential of singlet fission sensitizers in devices, it is necessary to understand and control the diffusion of the resultant triplet excitons. In this work, a new processing method is reported to systematically tune the intermolecular order and crystalline structure in films of a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn), without the need for chemical modifications. A combination of transient absorption spectroscopy and quantitative materials characterization enabled a detailed examination of the distance- and time-dependence of triplet exciton diffusion following singlet fission in these nanocrystalline TIPS-Pn films. Triplet-triplet annihilation rate constants were found to be representative of the weighted average of crystalline and amorphous phases in TIPS-Pn films comprising a mixture of phases. Adopting a diffusion model used to describe triplet-triplet annihilation, the triplet diffusion lengths for nanocrystalline and amorphous films of TIPS-Pn were estimated to be ∼75 and ∼14 nm, respectively. Importantly, the presence of even a small fraction (<10%) of the amorphous phase in the TIPS-Pn films greatly decreased the ultimate triplet diffusion length, suggesting that pure crystalline materials may be essential to efficiently harvest multiplied triplets even when singlet fission occurs on ultrafast time scales.
authors.affiliation: Department of Chemistry, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Christopher
authors.initials: C
authors.lastname: Grieco
authors.affiliation: Intercollege Materials Science and Engineering Program, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Grayson S
authors.initials: GS
authors.lastname: Doucette
authors.affiliation: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Ryan D
authors.initials: RD
authors.lastname: Pensack
authors.affiliation: Department of Chemistry, University of Kentucky , Lexington, Kentucky 40506, United States.
authors.forename: Marcia M
authors.initials: MM
authors.lastname: Payne
authors.affiliation: Department of Chemistry, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Adam
authors.initials: A
authors.lastname: Rimshaw
authors.affiliation: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Gregory D
authors.initials: GD
authors.lastname: Scholes
authors.affiliation: Department of Chemistry, University of Kentucky , Lexington, Kentucky 40506, United States.
authors.forename: John E
authors.initials: JE
authors.lastname: Anthony
authors.affiliation: Department of Chemistry, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.|Intercollege Materials Science and Engineering Program, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: John B
authors.initials: JB
authors.lastname: Asbury