The Role of Exciton Ionization Processes in Bulk Heterojunction Organic Photovoltaic Cells

Yunlong Zou, Russell J. Holmes

Research output: Contribution to journalArticlepeer-review

17 Scopus citations


To realize efficient photoconversion in organic semiconductors, photogenerated excitons must be dissociated into their constituent electronic charges. In an organic photovoltaic (OPV) cell, this is most often accomplished using an electron donor-acceptor (D-A) interface. Interestingly, recent work on MoOx/C60 Schottky OPVs has demonstrated that excitons in C60 may also undergo efficient bulk-ionization and generate photocurrent as a result of the large built-in field created by the MoOx/C60 interface. Here, it is demonstrated that bulk ionization processes also contribute to the short-circuit current density (JSC) and open-circuit voltage (VOC) in bulk heterojunction (BHJ) OPVs with fullerene-rich compositions. Temperature-dependent measurements of device performance are used to distinguish dissociation by bulk-ionization from charge transfer at the D-A interface. In optimized fullerene-rich BHJs based on the D-A pairing of boron subphthalocyanine chloride (SubPc)-C60, bulk-ionization is found to be responsible for ≈16% of the total photocurrent, and >30% of the photocurrent originating from C60. The presence of bulk-ionization in C60 also impacts the temperature dependence of VOC, with fullerene-rich SubPc:C60 BHJ OPVs showing a larger VOC than evenly mixed BHJs. The prevalence of bulk-ionization processes in efficient, fullerene-rich BHJs underscores the need to include these effects when engineering device design and morphology in OPVs.

Original languageEnglish (US)
Article number1500019
JournalAdvanced Energy Materials
Issue number12
StatePublished - Jun 1 2015

Bibliographical note

Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


  • Schottky cell
  • bulk heterojunctions
  • bulk ionization
  • open-circuit voltage
  • organic photovoltaic cells


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