Influence of Acceptor Structure on Barriers to Charge Separation in Organic Photovoltaic Materials Ryan D. Pensack†, Changhe Guo‡, Kiarash Vakhshouri‡, Enrique D. Gomez‡, and John B. Asbury*††‡ *† †Department of Chemistry and ‡Department of Chemical Engineering and the Materials Research Institute, The Pennsylvania State University

Background Charge Transfer States –Bound electron/hole pair at the interface of the donor and acceptor –CT state can be formed through electron transfer from donor to acceptor or hole transfer from acceptor to donor –The binding energy of this CT state is eV –Additional studies have shown that excess energy is not require to dissociate this CT state because of a minimal temperature dependence. Current work –Identify the factors that may influence charge separation in OPV materials using ultrafast vibrational spectroscopy –P3HT as the Donor –PC 61 BM and BTBP-PDI as acceptors –Measure the rates of CT state dissociation by using an approach based on solvatochromism assisted vibrational spectroscopy (SAVS)

Experimental SAVS (TRIR) –Films were prepared from chlorobenzene with nm thickness –Vis-IR experiment designed to only excite the donor –Probe with IR –1 ps resolution –50 mW/cm 2 power density X-Ray diffraction –Examine the crystalline nature of the films

Results: PDI P3HT:BTBP-PDI ultrafast C=O dynamics 300K –Broad feature contains positive polarons in P3HT, negative polarons in PDI and ground state bleach –Fit each of the three components and extract a center frequency for the bleach which is traced by the dotted line –Shift to lower energy is indicative of CT state dissociation Temperature Dependence on center frequency of the bleach –Cooler temperatures slow charge transfer dynamics

Results: PCBM Broad feature contains polarons and bleach 325 K –Extract bleach from 3 component fit –Bleach shift is must less sensitive than in PDI –Slower CT state dissociation (ns) Temperature Dependence –CT state dissociation is not sensitive to temperature –Nanosecond timescale at all temperatures

Asymptotic Behavior of Shifts G(t) represents experimental frequency shifts of the kinetic trace at a particular temperature G(∞) represents the asymptotic shifts at long times. –PDI: 1709 to 1705 cm -1 –PCBM: 1739 to 1740 cm -1 –Consistent with previous experiments with different donors –Likely the result of a thermal contraction of the donor –Origin of the greater sensitivity in PDI is currently under investigation

Film Morphology Crystalline P3HT in all films Amorphous PCBM and BTBP:PDI Crystalline C 8 :PDI

Reaction Barriers Plot reaction rate vs. 1/T PDI shows significant dependence but with non- arrhenius behavior –Extract a binding energy of 0.1eV PCBM shows no dependence indicating a barrierless pathway

BTBP:PDI Blend Barrier Conclude the charge separation is activated Time scale for CT state dissociation ranges from 1ps to 10ps depending on the temperature Excess energy model: Ground state, photosynthetic reaction centers –At lower temperature the dynamics are sufficiently slowed such that vibrational energy redistribution dissipates the energy before the CT state dissociates. Thus thermal energy is required. Competing Model –Authors believe the system is activated at all temperatures –Non-Arrhenius behavior arises from the dynamics being to fast to be clearly resolved. –The vibrational energy redistribution is much quicker in the excited state vs the ground state –Needs a faster experiment to make a confident assignment

PCBM Barrierless Separation Nanosecond timescale indicates excess energy does not play a role since it would be dissipated on that timescale Recent OPV device studies on the same blend do not show temperature dependence of the V OC Literature Insights –Electronic wave function of the PCBM is delocalized and the reorganization energy is less because of this delocalization –Molecular species show a larger coulombic attraction because of smaller spatial confinement of the charges –In PCBM, the wavefunctions are so delocalized that Coulombic barriers and reorganization energies are reduced below the energetic disorder of the system

Structure Influence on the Barrier PCBM –1 nm 3 volume and 60 carbon atoms to distribute the charge –Diffuse electron even if the charge is only on one fullerene –Non-directional because of the spherical symmetry of PCBM BTBP:PDI –20 atoms and 1/3 the volume of PCBM –Requires multiple PDI molecules to distribute the charge of the same spatial volume as compared with PCBM –The faster (1ps) charge separation PDI molecules; however, the lack of a crystalline phase prevents delocalization –The activation barrier combined with the lack of evidence of a crystalline phase suggests that electron localization causes a greater coulombic binding energy of the CT state –Exploring C 8 :PDI blend because of its crystallinity

Conclusion Examined the dynamics of OPV materials by monitoring the C=O vibration of photoreduced electron acceptors using TRIR The PCBM blend shows a barrierless dissociation of the CT state The BTBP:PDI requires energy to activate the CT state dissociation as indicated by the temperature dependence X-Ray measurements show the PCBM does not require an ordered phase to achieve sufficient charge delocalization The PDI acceptors may require a greater degree of crystallinity to achieve sufficient delocalization Proposed that C 8 :PDI blend would show less barriers to charge separation