Bulk heterojunction (BHJ) organic photovoltaic (OPV) is one of the most promising techniques to generate electricity with advantages of flexibility, solution processing and capability for large area device fabrication. Although the power conversion efficiency (PCE) of BHJ solar cells has already achieved over 13%, there are still problems remain to be solved. This thesis presents the binary and ternary organic BHJ devices with alternative donor:acceptor (D:A) ratios, and the charge transport properties and electronic interactions in their BHJ films. In a high performance BHJ solar cell, the commonly optimized D:A weight ratio is about 1:x, where x is commonly in excess of 1.5, when PC71BM is used as the acceptor. We demonstrated how to achieve high PCEs of BHJ solar cells by enriching the D:A weight ratios. The PCEs of the re-optimized cells were improved for the PTB7:PC71BM, PCDTBT:PC71BM, PDTSTPD:PC71BM devices. Current-voltage (JV) and admittance spectroscopy (AS) measurements indicate enhanced hole mobilities for the polymer-rich BHJs based on PTB7, PCDTBT, and PDTSTPD. At the same time, although the relative weight ratio of PC71BM is reduced, the electron mobilities are maintained due to the dispersion of fullerene domains by increased DIO concentrations. The active layer thickness of most optimized BHJ solar cells is about 100nm. The thin active layer is unfavorable for optical absorption and film coating. We employed a ternary strategy to address this problem, and the thick-film BHJ devices can retain 90% PCEs of their optimized thin-film devices. Three model systems were studied, involving PTB7:PC71BM, PTB7-Th:PC71BM and P3HT:PCBM BHJs. Into these BHJs, a ternary component, p-DTS(fbtth2)2 (DTS) is introduced. With DTS, the corresponding thick film devices have significantly improved PCEs. The ternary component DTS improves hole mobility and reduces sub-bandgap trap states. Both observations are well correlated with improved FFs of the ternary BHJ cells. Photothermal deflection spectroscopy (PDS) and 1H nuclear magnetic resonance (1H NMR) results indicate that DTS behaves as conducting bridges in between two neighboring polymer segments. Most lab-based BHJ solar cells are optimized by their power conversion efficiencies (PCEs). We challenge this conventional view by showing that BHJ cells using fullerene acceptors should be optimized by their fill-factors (FFs). With the optimized-FF approach, BHJ cells tend to have higher fullerene content when compared to the BHJ cells that are optimized by PCEs. The FF-optimized BHJ cells have slightly reduced PCEs (due to smaller Jscs) compared to the PCE-optimized cells. Yet, FF-optimized cells enjoy a much better thermal stability. We demonstrate that these FF-optimized BHJs possess better-balanced electron-to-hole mobility ratios due to weakly field-dependent electron mobilities. The improved mobility ratio suppresses carrier recombination. Our results suggest that BHJ cells optimized by their PCEs should be meta-stable, and other D:A ratios should be considered for practical BHJ cell development.

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Organic photovoltaic (OPV) is an exciting energy harvesting technique. Although its power conversion efficiency (PCE) now exceeds 10% in a research laboratory, the processing window of an OPV cell is still narrow. A fundamental understanding of the OPV materials is desired. This thesis presents the charge carrier transport properties and electronic interactions in the bulk heterojunction (BHJ) active layer of OPV cells. They were found to be well correlated with OPV device performances. Space-charge-limited current (SCLC) measurements and admittance spectroscopy (AS) were employed to study the charge transports, while photothermal deflection spectroscopy (PDS) was used to probe the trap densities inside the materials. Beneficial effects of a common solvent additive, 1,8-diiodooctance (DIO), on PTB7:PC71BM OPV cells have been investigated. With DIO present in the casting solution, the resulting BHJ films have much enhanced electron mobilities, whereas the impact on the hole mobility is negligible. The origin of increased electron mobility is the reduced average electron hopping distance for those films prepared with DIO solvent additive. A balance of hole-electron mobility by tuning the DIO concentration was demonstrated to be the way to optimize the OPV device performance. In light of carrier transport measurement results, a "polymer-rich" strategy with preserved device performance was demonstrated. After understanding the importance of balanced hole-electron mobility, the impact of donor-acceptor weight ratio on the performance of PTB7 : PC71BM based OPV cells was explored. Early stage electronic donor-acceptor interactions were revealed using ultra-low dosages of fullerenes. Before electron transport pathways percolate, the unconnected fullerene domains act as traps and hinder electron transport. From PDS, the trap density observed inside BHJ films was found to be anti-correlated with the fill factor of OPV devices. The origin of low FFs is mainly due to electron traps and localized states from fullerenes. Based on the observations, it is proposed that PC71BM tends to intercalate with PTB7 backbone instead of forming self-aggregates before the electron pathway percolation. Apart from investigating the fundamentals in OPV devices, a solution to improve its processing window was proposed in this thesis. Thermally stable polymer : fullerene OPV cells were fabricated by employing fluorenone-based solid additives. A charge transfer interaction between the additives and donor moiety of polymer formed a locked network which freezes the BHJ morphology under thermal stress. The most promising result retains 90% of the origin efficiency, upon thermal aging at 100 °C for more than 20 hours in PTB7:PC71BM solar cells. Besides fullerene-based OPV, all-polymer photovoltaic solar cells (all-PSCs) were also investigated. Two new difluorobenzene-naphthalene diimide based polymer electron acceptors, one random (P1) and one regioregular (P2) structure, were compared. P2 exhibited a much better molecular packing, a higher electron mobility and more balanced hole-electron mobilities in its composite film with polymer donor, PTB7-Th. An optimized PTB7-Th:P2 device can achieve a respectably high PCE over 5% for all-PSC devices. These all-PSCs should open a new avenue for next generation OPVs.