Although the field of polymer solar cell has seen much progress in device performance in the past few years, several limitations are holding back its further development. For instance, current high-efficiency (>9.0%) cells are restricted to material combinations that are based on limited donor polymers and only one specific fullerene acceptor. Here we report the achievement of high-performance (efficiencies up to 10.8%, fill factors up to 77%) thick-film polymer solar cells for multiple polymer:fullerene combinations via the formation of a near-ideal polymer:fullerene morphology that contains highly crystalline yet reasonably small polymer domains. This morphology is controlled by the temperature-dependent aggregation behaviour of the donor polymers and is insensitive to the choice of fullerenes. The uncovered aggregation and design rules yield three high-efficiency (>10%) donor polymers and will allow further synthetic advances and matching of both the polymer and fullerene materials, potentially leading to significantly improved performance and increased design flexibility.

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Fine energy-level modulations of small-molecule acceptors (SMAs) are realized via subtle chemical modifications on strong electron-withdrawing end-groups. The two new SMAs (IT-M and IT-DM) end-capped by methyl-modified dicycanovinylindan-1-one exhibit upshifted lowest unoccupied molecular orbital (LUMO) levels, and hence higher open-circuit voltages can be observed in the corresponding devices. Finally, a top power conversion efficiency of 12.05% is achieved.

The importance of morphology to organic solar cell performance is well known, but to date, the lack of quantitative, nanoscale and statistical morphological information has hindered obtaining direct links to device function. Here resonant X‐ray scattering and microscopy are combined to quantitatively measure the nanoscale domain size, distribution and composition in high efficiency solar cells based on PTB7 and PC71BM. The results show that the solvent additive diiodooctane dramatically shrinks the domain size of pure fullerene agglomerates that are embedded in a polymer‐rich 70/30 wt.% molecularly mixed matrix, while preserving the domain composition relative to additive‐free devices. The fundamental miscibility between the species – measured to be equal to the device's matrix composition – is likely the dominant factor behind the overall morphology with the additive affecting the dispersion of excess fullerene. As even the molecular ordering measured by X‐ray diffraction is unchanged between the two processing routes the change in the distribution of domain size and therefore increased domain interface is primarily responsible for the dramatic increase in device performance. While fullerene exciton harvesting is clearly one significant cause of the increase owing to smaller domains, a measured increase in harvesting from the polymer species indicates that the molecular mixing is not the reason for the high efficiency in this system. Rather, excitations in the polymer likely require proximity to a pure fullerene phase for efficient charge separation and transport. Furthermore, in contrast to previous measurements on a PTB7‐based system, a hierarchical morphology was not observed, indicating that it is not necessary for high performance.

A new copolymer PM6 based on fluorothienyl-substituted benzodithiophene is synthesized and characterized. The inverted polymer solar cells based on PM6 exhibit excellent performance with Voc of 0.98 V and power conversion efficiency (PCE) of 9.2% for a thin-film thickness of 75 nm. Furthermore, the single-junction semitransparent device shows a high PCE of 5.7%.

Two new soft X-ray scanning transmission microscopes located at the Advanced Light Source (ALS) have been designed, built and commissioned. Interferometer control implemented in both microscopes allows the precise measurement of the transverse position of the zone plate relative to the sample. Long-term positional stability and compensation for transverse displacement during translations of the zone plate have been achieved. The interferometer also provides low-distortion orthogonal x, y imaging. Two different control systems have been developed: a digital control system using standard VXI components at beamline 7.0, and a custom feedback system based on PC AT boards at beamline 5.3.2. Both microscopes are diffraction limited with the resolution set by the quality of the zone plates. Periodic features with 30 nm half period can be resolved with a zone plate that has a 40 nm outermost zone width. One microscope is operating at an undulator beamline (7.0), while the other is operating at a novel dedicated bending-magnet beamline (5.3.2), which is designed speci®cally to illuminate the microscope. The undulator beamline provides count rates of the order of tens of MHz at highenergy resolution with photon energies of up to about 1000 eV. Although the brightness of a bending-magnet source is about four orders of magnitude smaller than that of an undulator source, photon statistics limited operation with intensities in excess of 3 MHz has been achieved at high energy resolution and high spatial resolution. The design and performance of these microscopes are described.

Most optimized donor‐acceptor (D‐A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than ∼80% of incident photons with energies above the polymer's band gap. If the thickness of these devices could be increased without sacrificing internal quantum efficiency, the device power conversion efficiency (PCE) could be significantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐octylthieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) with 7.3% PCE and find that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge‐carrier recombination and limit device quantum efficiency. These findings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum efficiency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells.