Photooxidation of PC60BM: new insights from spectroscopy.

This joint experimental-theoretical spectroscopy study of the fullerene derivative PC60BM ([6,6]-phenyl-C60-butyric acid methyl ester) aims to improve the understanding of the effect of photooxidation on its electronic structure. We have studied spin-coated thin films of PC60BM by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, and Fourier Transform Infrared Spectroscopy (FTIR), before and after intentional exposure to simulated sunlight in air for different lengths of time. The π* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for the early changes to the fullerene cage, while FTIR spectra, in combination with O1s NEXAFS spectra, enabled the identification of the oxidation products. The changes observed in the spectra obtained by these complementary methods were compared with the corresponding Density Functional Theory (DFT) calculated single-molecule spectra of a large set of in silico generated oxidation products of PC60BM where oxygen atoms were attached to the C60 cage. This comparison confirms that photooxidation of PC60BM disrupts the conjugation of the fullerene cage by a transition from sp2 to sp3-hybridized carbon and causes the formation of several oxidation products, earlier proposed for C60. The agreement between experimental and calculated IR spectra suggests moreover the presence of dicarbonyl and anhydride structures on the fullerene cage, in combination with cage opening at the adsorption site. By including PC60BM with physisorbed O2 molecules on the cage in our theoretical description in order to model oxygen diffused through the film, the experimental O1s XPS and O1s NEXAFS spectra could be reproduced.

An experimental setup for dip-coating of thin films for organic solar cells under microgravity conditions.

We report the design and testing of a custom-built experimental setup for dip-coating from volatile solutions under microgravity conditions onboard an aircraft. Function and safety considerations for the equipment are described. The equipment proved to work well, both concerning the safety and the preparation of thin films. No leakage of the solvents, nor the solvent vapors, was detected, not even in a situation with a fluctuating gravitational field due to bad weather conditions. We have shown that the equipment can be used to prepare thin films of polymer blends, relevant for organic solar cells, from solution in a feasible procedure under microgravity conditions. The prepared films are similar to the corresponding films prepared under 1 g conditions, but with differences that can be related to the absence of a gravitational field during drying of the applied liquid coating. We report on some introductory results from the characterization of the thin films that show differences in film morphology and structure sizes.

Fine regulation of crystallisation tendency to optimize the BHJ nanostructure and performance of polymer solar cells.

Optimizing the nanostructure of the active layer of polymer solar cells (PSCs) is one of the main challenges to achieve high device performances. The phase separation of the donor polymer and molecular acceptor within the bulk heterojunction (BHJ) layer is often driven by the crystallisation of the acceptor molecules. Hence, a suitable crystallisation tendency of the chosen acceptor is ultimately important. In this work, we identified melting temperature as an indicator for the crystallisation tendency and introduced extended fused-aromatic rings to the end groups of the nonfullerene acceptor molecule to enhance the intermolecular binding energy as well as its crystallisation tendency. The crystallinity, crystal regularity and average crystal size were significantly increased for those molecules with larger fused end groups. The devices containing molecule IDTTC with two fused thiophene rings, which displayed intermediate crystallisation tendency, were found to possess an optimized phase separation scale, balanced hole/electron mobility and highest device performances with the fill factor as high as 73.2% and a power conversion efficiency of 13.49%. With the above observations, we established a new route and paradigm to adjust the crystallisation tendency and BHJ nanostructure of nonfullerene acceptor molecules, thus enhancing the device performances through molecular engineering.

Impact of intentional photo-oxidation of a donor polymer and PC70BM on solar cell performance.

A short lifetime is the main factor hindering the wider implementation of low-cost organic photovoltaics in large-area and outdoor applications. Ingress of oxygen and water vapour through non-ideal encapsulation layers is a known cause of degradation for polymer/fullerene based solar cells. To better understand the origin of this performance degradation, we study the effect of intentional exposure of the photo-active layer to simulated sunlight (AM1.5) in air both on the solar cell performance and on the molecular semiconductor materials. Cathode-free thin films of a blend of the electron donor polymer poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and the electron acceptor fullerene derivative [6,6]-phenyl-C70-butyric acid methyl ester (PC70BM) were exposed to simulated sunlight in air. Fourier-transform infrared spectra demonstrate the formation of carbonyl photo-oxidation products in the blend films, as well as in the pristine polymer and fullerene films. Solar cells prepared with photo-oxidized active layers show increasingly degraded electrical performance (lower short circuit current, open circuit voltage and fill factor) with increasing exposure time. The increased diode ideality factor indicates that trap-assisted recombination hinders device operation after exposure. The external quantum efficiency decreases drastically with increasing exposure time over the whole photon energy range, while the UV-vis absorption spectra of the blend films only show a mild photo-induced bleaching. This demonstrates that not only the photo-induced degradation of the solar cell performance is not predominantly caused by the loss in light absorption, but charge transport and collection are also hampered. This is explained by the fact that photo-oxidation of PC70BM causes bonds in its conjugated cage to break, as evidenced by the decreased π* intensity in C1s-NEXAFS spectra of PC70BM films. This degradation of unoccupied states of PC70BM will hinder the transport of photo-generated electrons to the electrode. Surface photovoltage spectroscopy gives direct evidence for gap states at the surface of a PC70BM film, formed after 2 hours of exposure and resulting in upward band bending at the PC70BM/air surface. These observations indicate that the photo-oxidation of PC70BM is likely to be the main cause of the performance degradation observed when the photoactive layer of a TQ1:PC70BM solar cell is intentionally exposed to light in air.

Photo-degradation in air of the active layer components in a thiophene-quinoxaline copolymer:fullerene solar cell.

We have studied the photo-degradation in air of a blend of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1), and how the photo-degradation affects the solar cell performance. Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, changes to the electronic structure of TQ1 and PCBM caused by illumination in ambient air are investigated and compared between the pristine materials and the blend. The NEXAFS spectra show that the unoccupied molecular orbitals of TQ1 are not significantly changed by the exposure of pristine TQ1 to light in air, whereas those of PCBM are severely affected as a result of photo-induced degradation of PCBM. Furthermore, the photo-degradation of PCBM is accelerated by blending it with TQ1. While the NEXAFS spectrum of TQ1 remains unchanged upon illumination in air, its valence band spectrum shows that the occupied molecular orbitals are weakly affected. Yet, UV-Vis absorption spectra demonstrate photo-bleaching of TQ1, which is attenuated in the presence of PCBM in blend films. Illumination of the active layer of TQ1:PCBM solar cells prior to cathode deposition causes severe losses in electrical performance.