Charge-Transfer State Dynamics Following Hole and Electron Transfer in Organic Photovoltaic Devices.
The formation of bound electron-hole pairs, also called charge-transfer (CT) states, in organic-based photovoltaic devices is one of the dominant loss mechanisms hindering performance. Whereas CT state dynamics following electron transfer from donor to acceptor have been widely studied, there is not much known about the dynamics of bound CT states produced by hole transfer from the acceptor to the donor. In this letter, we compare the dynamics of CT states formed in the different charge-transfer pathways in a range of model systems. We show that the nature and dynamics of the generated CT states are similar in the case of electron and hole transfer. However the yield of bound and free charges is observed to be strongly dependent on the HOMOD-HOMOA and LUMOD-LUMOA energy differences of the material system. We propose a qualitative model in which the effects of static disorder and sampling of states during the relaxation determine the probability of accessing CT states favorable for charge separation.
†FOM Institute AMOLF, Science Park 104, Amsterdam, The Netherlands.|‡Cavendish Laboratory, University of Cambridge, JJ Thomson Ave, Cambridge CB3 0HE, United Kingdom.
Artem A
AA
Bakulin
§Centre for Plastic Electronics, Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom.
Stoichko D
SD
Dimitrov
‡Cavendish Laboratory, University of Cambridge, JJ Thomson Ave, Cambridge CB3 0HE, United Kingdom.
Akshay
A
Rao
‡Cavendish Laboratory, University of Cambridge, JJ Thomson Ave, Cambridge CB3 0HE, United Kingdom.
Philip C Y
PC
Chow
§Centre for Plastic Electronics, Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom.
Christian B
CB
Nielsen
§Centre for Plastic Electronics, Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom.
Bob C
BC
Schroeder
§Centre for Plastic Electronics, Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom.
Iain
I
McCulloch
†FOM Institute AMOLF, Science Park 104, Amsterdam, The Netherlands.
Huib J
HJ
Bakker
§Centre for Plastic Electronics, Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom.
James R
JR
Durrant
‡Cavendish Laboratory, University of Cambridge, JJ Thomson Ave, Cambridge CB3 0HE, United Kingdom.
Richard H
RH
Friend
IR spectroscopy; charge separation; charge trapping; conjugated polymers; organic solar cells; ultrafast spectroscopy