Graphene modified indium tin oxide electrodes for organic solar cells
Creators: name: Chang, Ci'En Sharon
Publisher: name: Imperial College London
Year: 2014

description: In this thesis, we explore the use of graphene incorporated onto indium tin oxide (G/ITO) as a structural template to modify the orientation of copper phthalocyanine (CuPc) molecules for organic photovoltaic (OPV) device applications. We also investigate the effectiveness of 2,3,5,65 tetrafluoro57,7,8,85tetracyanoquinodimethane (F45TCNQ) as a work function modifier for G/ITO without compromising the templating properties of graphene. Photoemission spectroscopy (PES) is employed to assess the electronic properties at the anode5CuPc interface, while X5ray diffraction (XRD) and near5edge X5ray absorption fine structure (NEXAFS) are used to determine the molecular orientation of CuPc. OPV devices are fabricated to attempt to correlate the observations at the microscopic level with the macroscopic device performance. First, we investigate the electronic properties of CuPc deposited on G/ITO and ITO using PES. While the interaction between CuPc molecules and ITO and G/ITO is similar, the hole injection barrier (HIB) is ~0.9 eV for CuPc/G/ITO as compared to 0.5 eV for CuPc/ITO. Therefore, further modification of G/ITO to reduce the HIB is required. The XRD spectrum of CuPc molecules deposited onto graphene grown on copper foil (G/Cu) verifies that graphene is an effective structural template, causing CuPc molecules to ‘lie’ on the substrate. NEXAFS data shows that the orientation of CuPc molecules changes from ‘standing’ on ITO to ‘tilted’ on G/ITO. Next, the effectiveness of F45TCNQ deposited on ITO and G/ITO as a work function modifier is assessed. A thin layer of F45TCNQ is able to increase the substrate work function to ~5 eV, which is close to the ionization potential of CuPc molecules. This suggests that barrierless extraction of holes from CuPc into F45TCNQ modified ITO or G/ITO may be possible. F45TCNQ molecules are found to be predominantly tilted on G/ITO, suggesting that the templating property of graphene may be propagated through F45TCNQ molecules. CuPc molecules deposited onto F45 TCNQ/G/ITO attain a ‘lying’ configuration, confirming that the templating property of graphene is preserved despite the inclusion of a layer of F45TCNQ. The HIB is dramatically reduced to ~0.2 eV for CuPc/F45TCNQ/G/ITO, and ~0.1 eV for CuPc/F45TCNQ/ITO. Optical absorption of templated CuPc molecules over the visible range is enhanced by over 40% as compared to the non5templated molecules. Therefore, the structure of F45TCNQ/G/ITO appears to be a potential anode design to improve OPV device performance. Our test cells however do not show an improvement in OPV parameters due to the poor quality of transferred graphene, and the high series resistance in our unoptimized OPV device. Finally, the diffusion of F45TCNQ through a CuPc film is studied using time5of5flight secondary ion mass spectrometry (TOF5SIMS). The F5 depth profiles establish that a higher quantity of F45 TCNQ molecules diffuse into CuPc on the G/ITO sample. This is attributed to the weaker interfacial adhesion between F45TCNQ and graphene, and the crystallinity of the templated CuPc film. The quantity of diffused F45TCNQ in the G/ITO sample is only about 0.2 mol%. At this dopant concentration, the conductivity of the film should increase; thus doping of the whole organic film may be favourable for OPV devices.