Anthony J. Petty

Endothermic singlet fission is hindered by excimer formation

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

Elucidation of Excitation Energy Dependent Correlated Triplet Pair Formation Pathways in an Endothermic Singlet Fission System

Singlet fission is the spin-allowed conversion of a photogenerated singlet exciton into two triplet excitons in organic semiconductors, which could enable single-junction photovoltaic cells to break the Shockley-Queisser limit. The conversion of singlets to free triplets is mediated by an intermediate correlated triplet pair (TT) state, but an understanding of how the formation and dissociation of these states depend on energetics and morphology is lacking. In this study, we probe the dynamics of TT states in a model endothermic fission system, TIPS-Tc nanoparticles, which show a mixture of crystalline and disordered regions. We observe the formation of different TT states, with varying yield and different rates of singlet decay, depending on the excitation energy. An emissive TT state is observed to grow in over 1 ns when excited at 480 nm, in contrast to excitation at lower energies where this emissive TT state is not observed. This suggests that the pathway for singlet fission in these nanoparticles is strongly influenced by the initial sub-100 fs relaxation of the photoexcited state away from the Franck-Condon point, with multiple possible TT states. On nanosecond time scales, the TT states are converted to free triplets, which suggests that TT states might diffuse into the disordered regions of the nanoparticles where their breakup to free triplets is favored. The free triplets then decay on μs time scales, despite the confined nature of the system. Our results provide important insights into the mechanism of endothermic singlet fission and the design of nanostructures to harness singlet fission.

Understanding the Crystal Packing and Organic Thin-Film Transistor Performance in Isomeric Guest–Host Systems

In order to understand how additives influence the structure and electrical properties of active layers in thin-film devices, a compositionally identical but structurally different guest-host system based on the syn and anti isomers of triethylsilylethynyl anthradithiophene (TES ADT) is systematically explored. The mobility of organic thin-film transistors (OTFTs) comprising anti TES ADT drops with the addition of only 0.01% of the syn isomer and is pinned at the mobility of OTFTs having pure syn isomer after the addition of only 10% of the isomer. As the syn isomer fraction increases, intermolecular repulsion increases, resulting in a decrease in the unit-cell density and concomitant disordering of the charge-transport pathway. This molecular disorder leads to an increase in charge trapping, causing the mobility of OTFTs to drop with increasing syn-isomer concentration. Since charge transport is sensitive to even minute fractions of molecular disorder, this work emphasizes the importance of prioritizing structural compatibility when choosing material pairs for guest-host systems.

Singlet Fission and Triplet Transfer to PbS Quantum Dots in TIPS-Tetracene Carboxylic Acid Ligands.

Singlet exciton fission allows for the generation of two triplet excitons for each photon absorbed within an organic semiconductor. Efficient harvesting of these triplets could allow for the Shockley-Queisser limit on the power conversion efficiency of single-junction photovoltaics to be broken. Here, we show that singlet fission molecules bound directly to PbS quantum dots as ligands can undergo singlet fission with near unity efficiency and can transfer triplets sequentially into the PbS with near unity efficiency. Within the PbS, the excitations recombine, giving rise of the emission of photons. This allows for the doubling of the quantum dot photoluminescence quantum efficiency when photons are absorbed by the singlet fission ligand, as compared to when directly absorbed in the quantum dot. Our approach demonstrates that it is possible to convert the exciton multiplication process of singlet fission into a photon multiplication process and provides a new path to harness singlet fission with photovoltaics.

Supporting data for "Elucidation of Excitation Energy Dependent Correlated Triplet Pair Formation Pathways in an Endothermic Singlet Fission System"

Data supporting the experimental claims of this publication helps inestablishing formation pathways of intermediates formed during the process of singlet fission. Data includes that from steady state and transient absorption, photoluminescence measurements, structural information from electron microscopy etc.

Presence of Short Intermolecular Contacts Screens for Kinetic Stability in Packing Polymorphs

Polymorphism is pervasive in molecular solids. While computational predictions of the molecular polymorphic landscape have improved significantly, identifying which polymorphs are preferentially accessed and experimentally stable remains a challenge. We report a framework that correlates short intermolecular contacts with polymorphic stability. The presence of short contacts between neighboring molecules prevents structural rearrangement and stabilizes the packing arrangement, even when the stabilized polymorph is not enthalpically favored. In the absence of such intermolecular short contacts, the molecules have added degrees of freedom for structural rearrangement, and solid-solid polymorphic transformations occur readily. Starting with a series of core-halogenated naphthalene tetracarboxylic diimides, we establish this framework with the packing polymorphs of more than 20 compounds, ranging from molecular semiconductors to pharmaceutics and biological building blocks. This framework, widely applicable across molecular solids, can help refine computational predictions by identifying the polymorphs that are kinetically stable.

CCDC 1481034: Experimental Crystal Structure Determination

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