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1 March 2010Ultrafast terahertz spectroscopy for measuring carrier dynamics in nanoscale photovoltaic materials
Femtosecond pump-probe methods are useful tools for investigating transient electronic and vibrational states of
conducting materials and molecular photochemistry. Ultraviolet and visible excitation pulses (<150 fs, <20 μJ, 400-800
nm) with time-delayed broadband terahertz (~500 GHz to 3 THz) probing pulses (Time-Resolved Terahertz
Spectroscopy; TRTS) are used to measure linear spectroscopic transmission changes resulting from exciton and free
carrier population in organic semiconducting thin films. Picosecond timescale exciton geminate recombination and
longer-time free-carrier conduction in semiconductor polymers and nanolayered donor-acceptor films are discussed.
Systems investigated with terahertz probe pulses include thiophene-based polymers (P3HT, PBTTT) studied as drop and
spin-cast films on transparent quartz substrates. The relative conductivity of these films increases with increasing P3HT
polymer molecular weight, structural regularity, and the fused rings in PBTTT further increases conduction. Recent
studies of composite and nanolayered films (by vapor deposition) containing alternating Zn-phthalocyanine (ZnPc) and
buckminsterfullerene (C60) also yield high conduction that scales linearly with the number of interfaces and total film
thickness. We find evidence for a short-lived charge transfer state of C60 that decays within several picoseconds of
excitation. In contrast, both composite and multilayered films exhibit long-lived THz dynamics that depends on the
composition and structure of the films. The optimum composition for charge transfer within composite films is observed
for a ~1:1 blend of ZnPc with C60 and a 4:1 blend of P3HT with Phenyl C61 Butyric Acid Methyl Ester (PCBM) while an
increase in charge photo-generation with decreasing layer thickness (2 nm) exhibits the strongest THz signal. These
findings parallel results for FET polymer transistor devices pointing to the advantage of optically measuring material
properties before device test.
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Okan Esenturk, Paul A. Lane, Joseph S. Melinger, Edwin J. Heilweil, "Ultrafast terahertz spectroscopy for measuring carrier dynamics in nanoscale photovoltaic materials," Proc. SPIE 7600, Ultrafast Phenomena in Semiconductors and Nanostructure Materials XIV, 76000I (1 March 2010); https://doi.org/10.1117/12.843636