So far, one of the fundamental limitations of organic photovoltaic (OPV) device power conversion efficiencies (PCEs) has been the low voltage output caused by a molecular orbital mismatch between the donor polymer and acceptor molecules. Here, we present a means of addressing the low voltage output by introducing novel trimetallic nitride endohedral fullerenes (TNEFs) as acceptor materials for use in photovoltaic devices. TNEFs were discovered in 1999 by Stevenson et al. ; for the first time derivatives of the TNEF acceptor, Lu(3)N@C(80), are synthesized and integrated into OPV devices. The reduced energy offset of the molecular orbitals of Lu(3)N@C(80) to the donor, poly(3-hexyl)thiophene (P3HT), reduces energy losses in the charge transfer process and increases the open circuit voltage (Voc) to 260 mV above reference devices made with [6,6]-phenyl-C(61)-butyric methyl ester (C(60)-PCBM) acceptor. PCEs >4% have been observed using P3HT as the donor material. This work clears a path towards higher PCEs in OPV devices by demonstrating that high-yield charge separation can occur with OPV systems that have a reduced donor/acceptor lowest unoccupied molecular orbital energy offset.
Here the influence that 1‐(3‐hexoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐Lu3N@C81, Lu3N@C80–PCBH, a novel acceptor material, has on active layer morphology and the performance of organic photovoltaic (OPV) devices using this material is reported. Polymer/fullerene blend films with poly(3‐hexylthiophene), P3HT, donor material and Lu3N@C80–PCBH acceptor material are studied using absorption spectroscopy, grazing incident X‐ray diffraction and photocurrent spectra of photovoltaic devices. Due to a smaller molecular orbital offset the OPV devices built with Lu3N@C80–PCBH display increased open circuit voltage over empty cage fullerene acceptors. The photovoltaic performance of these metallo endohedral fullerene blend films is found to be highly impacted by the fullerene loading. The results indicate that the optimized blend ratio in a P3HT matrix differs from a molecular equivalent of an optimized P3HT/[6,6]‐phenyl‐C61‐butyric methyl ester, C60–PCBM, active layer, and this is related to the physical differences of the C80 fullerene. The influence that active layer annealing has on the OPV performance is further evaluated. Through properly matching the film processing and the donor/acceptor ratio, devices with power conversion efficiency greater than 4% are demonstrated.
Fiber-optic probes are widely used in optical spectroscopy of biological tissues and other turbid media. Only limited information exists, however, on the ways in which the illumination-collection geometry and the overall probe design influence the interrogation of media. We have investigated both experimentally and computationally the effect of probe-to-target distance (PTD) on the diffuse reflectance collected from an isotropically (Lambertian) scattering target and an agar-based tissue phantom. Studies were conducted with three probes characterized by either common (single-fiber) or separate (two bifurcated multifiber probes) illumination and collection channels. This study demonstrates that PTD, probe design, and tissue scattering anisotropy influence the extent of the transport of light into the medium, the light-collection efficiency, and the sampling volume of collected light. The findings can be applied toward optimization of fiber-optic probe designs for quantitative optical spectroscopy of turbid media including biological tissues.
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