Free Carrier Generation in Fullerene Acceptors and Its Effect on Polymer Photovoltaics

Early research on C60 led to the discovery that the absorption of photons with energy greater than 2.35 eV by bulk C60 produces free charge carriers at room temperature. We find that not only is this also true for many of the soluble fullerene derivatives commonly used in organic photovoltaics, but also that the presence of these free carriers has significant implications for the modeling, characterization, and performance of devices made with these materials. We demonstrate that the discrepancy between absorption and quantum efficiency spectra in P3HT:PCBM is due to recombination of such free carriers in large PCBM domains before they can be separated at a donor/acceptor interface. Since most theories assume that all free charges result from the separation of excitons at a donor/acceptor interface, the presence of free carrier generation in fullerenes can have a significant impact on the interpretation of data generated by numerous field-dependent techniques.

[1]  K. Haenen,et al.  Absorption phenomena in organic thin films for solar cell applications investigated by photothermal deflection spectroscopy , 2005 .

[2]  H. Byrne,et al.  Comprehensive analysis of intermolecular charge-transfer excited states in C 60 and C 70 films , 1998 .

[3]  F. Würthner,et al.  Field-dependent exciton dissociation in organic heterojunction solar cells , 2012 .

[4]  Thomas Kirchartz,et al.  Recombination via tail states in polythiophene:fullerene solar cells , 2011 .

[5]  Thuc‐Quyen Nguyen,et al.  Quantification of Geminate and Non‐Geminate Recombination Losses within a Solution‐Processed Small‐Molecule Bulk Heterojunction Solar Cell , 2012, Advanced materials.

[6]  E. Hoke,et al.  Incomplete exciton harvesting from fullerenes in bulk heterojunction solar cells. , 2009, Nano letters.

[7]  Mats Andersson,et al.  Quantification of Quantum Efficiency and Energy Losses in Low Bandgap Polymer:Fullerene Solar Cells with High Open‐Circuit Voltage , 2012 .

[8]  Zhe Li,et al.  Phase-Dependent Photocurrent Generation in Polymer/Fullerene Bulk Heterojunction Solar Cells , 2011 .

[9]  C. Deibel,et al.  Charge carrier extraction by linearly increasing voltage: Analytic framework and ambipolar transients , 2010, 1006.4394.

[10]  Takuji Adachi,et al.  Ultralong-Range Polaron-Induced Quenching of Excitons in Isolated Conjugated Polymers , 2011, Science.

[11]  Yang Yang,et al.  Origin of photomultiplication in C60 based devices , 2007 .

[12]  Sei‐Yong Kim,et al.  Photoconductivity of C60 as an Origin of Bias‐Dependent Photocurrent in Organic Photovoltaics , 2012 .

[13]  Jenny Nelson,et al.  Polymer:fullerene bulk heterojunction solar cells , 2011 .

[14]  Juliane Kniepert,et al.  Photogeneration and Recombination in P3HT/PCBM Solar Cells Probed by Time-Delayed Collection Field Experiments , 2011 .

[15]  Charles E. Swenberg,et al.  Electronic Processes in Organic Crystals , 1982 .

[16]  Alberto Salleo,et al.  Controlled conjugated backbone twisting for an increased open-circuit voltage while having a high short-circuit current in poly(hexylthiophene) derivatives. , 2012, Journal of the American Chemical Society.

[17]  J. Nelson,et al.  Extracting Microscopic Device Parameters from Transient Photocurrent Measurements of P3HT:PCBM Solar Cells , 2012 .

[18]  Priya J. Jadhav,et al.  High efficiency organic multilayer photodetectors based on singlet exciton fission , 2009 .

[19]  J. Jortner Collisions of Singlet Excitons in Molecular Crystals , 1968 .

[20]  C. Deibel,et al.  Photocurrent in bulk heterojunction solar cells , 2010, 1001.2546.

[21]  J. Hornig,et al.  Multiple‐Charge‐Carrier Generation Processes in Anthracene , 1965 .

[22]  Tracey M. Clarke,et al.  Charge photogeneration in organic solar cells. , 2010, Chemical reviews.

[23]  V. Mihailetchi,et al.  Photocurrent generation in polymer-fullerene bulk heterojunctions. , 2004, Physical review letters.

[24]  J. Kǒcka,et al.  Extraction current transients: new method of study of charge transport in microcrystalline silicon , 2000, Physical review letters.

[25]  P. Blom,et al.  Unified description of charge-carrier mobilities in disordered semiconducting polymers. , 2005, Physical review letters.

[26]  J. Simmons,et al.  Basic equations for statistics, recombination processes, and photoconductivity in amorphous insulators and semiconductors , 1972 .