Singlet, triplet, electron and hole transport along single polymer chains

The diffusion of singlet and triplet excitons along single polyfluorene chains in solution has been studied by monitoring their transport to end traps. Time-resolved transient absorption and steady state fluorescence were used to determine fractions of excitons that reach the end caps. In order to accurately determine the singlet diffusion coefficient, the fraction of polymer ends that have end traps was determined through a combination of NMR and triplet quenching experiments. The distributions of polymer lengths were also taken into account and the resulting analysis points to a surprisingly long singlet diffusion length of 34 nm. Experiments on triplet transport also suggest that the entire 100nm+ chain is accessible to the triplet during its lifetime suggesting a lack of hindrance by defects or traps on this timescale. Time Resolved Microwave Conductivity measurements were also performed on a series of different length oligo- and polyfluorenes in solution allowing a global fit to be performed to extract an accurate intrachain mobility of 1.1 cm2/Vs.

[1]  J. Warman,et al.  The study of primary and secondary charge carriers in nanosecond pulse irradiated liquid dielectrics using a resonant microwave cavity , 1977 .

[2]  Andrew R. Cook,et al.  The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory , 2004 .

[3]  Donal D. C. Bradley,et al.  Chain geometry, solution aggregation and enhanced dichroism in the liquidcrystalline conjugated polymer poly(9,9-dioctylfluorene) , 1998 .

[4]  John R. Miller,et al.  Transport of Triplet Excitons along Continuous 100 nm Polyfluorene Chains. , 2015, The journal of physical chemistry. B.

[5]  T. Iyoda,et al.  Electron and hole transport to trap groups at the ends of conjugated polyfluorenes. , 2008, Journal of the American Chemical Society.

[6]  E. C. Zachmanoglou,et al.  Introduction to partial differential equations with applications , 1976 .

[7]  John R. Miller,et al.  Mobility of Holes in Oligo- and Polyfluorenes of Defined Lengths , 2014 .

[8]  R. Kubo Statistical-Mechanical Theory of Irreversible Processes : I. General Theory and Simple Applications to Magnetic and Conduction Problems , 1957 .

[9]  J. C. Jaeger,et al.  Conduction of Heat in Solids , 1952 .

[10]  J. Warman,et al.  The study of the transient conductivity of pulse irradiated dielectric liquids on a nanosecond timescale using microwaves , 1977 .

[11]  P. Blom,et al.  Exciton diffusion in organic semiconductors , 2015 .

[12]  J. Schins,et al.  Frequency dependent mobility of charge carriers along polymer chains with finite length , 2006 .

[13]  U. Scherf,et al.  Charge Transport along Coiled Conjugated Polymer Chains , 2007 .

[14]  Seogjoo J. Jang,et al.  Triplet Transport to and Trapping by Acceptor End Groups on Conjugated Polyfluorene Chains , 2011 .

[15]  Qin Wu,et al.  Charge Transfer Fluorescence and 34 nm Exciton Diffusion Length in Polymers with Electron Acceptor End Traps. , 2015, The journal of physical chemistry. B.

[16]  John R. Miller,et al.  Role of bad dihedral angles: methylfluorenes act as energy barriers for excitons and polarons of oligofluorenes. , 2014, The journal of physical chemistry. A.