Improving Device Efficiencies in Organic Photovoltaics through the Manipulation of Device Architectures and the Development of Low-Bandgap Materials
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Over the past two decades, vast amounts of research have been conducted in the pursuit of suitable organic semiconductors to replace inorganic materials in electronic applications due to their advantages of being lightweight, flexible, and solution-processible. However, before organic photovoltaics (OPVs) can be truly competitive and commercially viable, their efficiencies must be improved significantly. In this examination, we pursue higher efficiency OPVs in two different ways. Our attempts focus on 1) altering the microstructure of devices to improve charge dissociation, charge transport, and our understanding of how these devices function, and 2) tailoring materials to achieve optimal band gaps and energy levels for use in organic electronics. First, we demonstrate how the vertical morphology of bulk heterojunction (BHJ) solar cells, with an active layer consisting of self-assembled poly(3-hexylthiophene) (P3HT) nanowires and (6,6)-phenyl C<sub>61</sub>-butyric acid methyl ester (PCBM), can be beneficially influenced. Most device fabrication routes using similar materials employ an annealing step to influence active layer morphology, but this process can create an unfavorable phase migration where P3HT is driven toward the cathode. In contrast, we demonstrate devices that exhibit an increase in relative fullerene concentration at the top of the active layer by introducing the donor phase as a solid nanowire in the active layer solution and altering the pre-spin drying time. X-ray photoelectron spectroscopy (XPS) and conductive and photoconductive atomic force microscopy (cAFM and pcAFM) provide detailed information about how the surface of the active layer can be influenced; this is done by tracking the concentration and alignment of P3HT and PCBM domains. Using this new procedure, devices are made with power conversion efficiencies surpassing 2%. Additionally, we show that nanowires grown in the presence of the fullerene perform differently than those that are grown and mixed separately; exposure to the nanowire during self-assembly may allow the fullerene to coat nanowire surfaces and influence the photocurrent within the device. Furthermore, because we are able to carefully control the regioregularity of our P3HT, we are able to produce a series of nanowires with regioregularities ranging between 93% and 99%. X-ray diffraction (XRD) shows that as the regioregularity of the polymer increases, the coherent domain size along the long-axis of the nanowires also becomes larger. When organic field effect transistors (OFETs) are made from these materials, the hole mobility of the nanowire films also has a positive correlation with regioregularity. As the domains within the nanowires grow larger, the frequency of domain boundaries decreases, allowing charges to percolate more efficiently along the nanowire. Additionally, we show that by introducing C<sub>60</sub> into the active layer of P3HT:PCBM devices, we can modulate the crystal habit of the PCBM domains. Using optical microscopy and UV-vis absorption spectroscopy, we demonstrate that C<sub>60</sub> additions alter the crystal morphology and greatly reduce the size of fullerene crystallites that are observed after extended annealing times and under aggressive aging conditions. We also show by fabricating organic field-effect transistors (OFETs) from PCBM:C<sub>60</sub> blends that the incorporation of C<sub>60</sub> does not adversely affect the electron mobility in these films. Finally, we show that as C<sub>60</sub> is incorporated into P3HT:PCBM OPVs, devices become more thermally stable and do not degrade in performance as rapidly as traditional P3HT:PCBM blends. Lastly, the synthesis of four alternating copolymers using benzo[2,1-b;3,4-b’]dithiophene (BDP) as the common donor unit is presented. Incorporating BDP, which consists of fused dithiophene units with a benzene ring, into these polymers should produce a low-lying highest occupied molecular orbital (HOMO) energy level. Low-lying HOMO levels are desirable to produce high open circuit voltages (V<sub>OC</sub>) in organic BHJ photovoltaic devices. The preliminary results of their performance in solar cells, using PCBM as the electron acceptor, is presented. The V<sub>OC</sub> values follow the expected trend: increasing with decreasing HOMO level of the polymer. High V<sub>OC</sub> values of 0.81 and 0.82 V have been obtained from two polymers: PBDPBT and PBDPDPP. The highest initial power conversion efficiency (PCE) achieved in these unoptimized devices was 1.11% due to relatively low J<sub>SC</sub> values. The variation observed in the J<sub>SC</sub> values between the four polymers is discussed. Device performance is expected to increase with optimization of processing conditions for the devices.