Suren A. Gevorgyan

Organic photovoltaics (OPVs) evolve in an exponential manner in the two key areas of efficiency and stability. The power conversion efficiency (PCE) has in the last decade been increased by almost a factor of ten approaching 10%. A main concern has been the stability that was previously measured in minutes, but can now, in favorable circumstances, exceed many thousands of hours. This astonishing achievement is the subject of this article, which reviews the developments in stability/degradation of OPVs in the last five years. This progress has been gained by several developments, such as inverted device structures of the bulk heterojunction geometry device, which allows for more stable metal electrodes, the choice of more photostable active materials, the introduction of interfacial layers, and roll-to-roll fabrication, which promises fast and cheap production methods while creating its own challenges in terms of stability.

An inverted polymer solar cell geometry comprising a total of five layers was optimized using laboratory scale cells and the operational stability was studied under model atmospheres. The device geometry was substrate-ITO-ZnO-(active layer)-PEDOT:PSS-silver with P3HT-PCBM as the active layer. The inverted devices were compared to model devices with a normal geometry where the order of the layers was substrate-ITO-PEDOT:PSS-(active layer)-aluminium. In both cases illumination was through the substrate which requires that it is transparent. Both device types were optimized to a power conversion efficiency of 2.7% (1000 W m−2, AM1.5G, 72 ± 2 °C). The devices were operated under illumination while being subjected to different atmospheres to identify the dominant modes of degradation. Dry nitrogen (99.999%), dry oxygen (99.5%), humid nitrogen (90 ± 5% relative humidity) and ambient atmosphere (20% oxygen, 20 ± 5% relative humidity) were employed and both device types were found to be stable in a nitrogen atmosphere during the test period of 200 hours. The devices with a normal geometry where an aluminium electrode is employed gave stable operation in dry oxygen but did not give stable device operation in the presence of humidity. The inverted devices behaved oppositely where the less reactive silver electrode gave stable operation in the presence of humidity but poor stability in the presence of oxygen. The inverted model device was then used to develop a new process giving access to fully roll-to-roll (R2R) processed polymer solar cells entirely by solution processing starting from a polyethyleneterephthalate (PET) substrate with a layer of indium-tin-oxide (ITO). All processing was performed in air without vacuum coating steps and modules comprising eight serially connected cells gave power conversion efficiencies as high as 2.1% for the full module with 120 cm2 active area (AM1.5G, 393 W m−2) and up to 2.3% for modules with 4.8 cm2 active area (AM1.5G, 1000 W m−2).

The spatial distribution of reaction products in multilayer polymer solar cells induced by water and oxygen atmospheres was mapped and used to elucidate the degradation patterns and failure mechanisms in an inverted polymer solar cell. The active material comprised a bulk heterojunction formed by poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) sandwiched between a layer of zinc oxide and a layer of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) that acted as, respectively, electron and hole transporting layers between the active material and the two electrodes indium-tin-oxide (ITO) and printed silver. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) in conjunction with isotopic labeling using H(2)(18)O and (18)O(2) enabled detailed information on where and to what extent uptake took place. A comparison was made between the use of a humid (oxygen-free) atmosphere and a dry oxygen atmosphere during testing of devices that were kept in the dark and devices that were subjected to illumination under simulated sunlight. It was found that the reactions taking place at the interface between the active layer and the PEDOT:PSS were the major cause of device failure in the case of these inverted devices, which are compatible with full roll-to-roll (R2R) coating and industrial manufacture. The PEDOT:PSS was found to phase separate, with the PEDOT-rich phase being responsible for most of the interface degradation in oxygen atmospheres. In water atmospheres, little chemically induced degradation was observed, whereas a large partially reversible dependence of the open circuit voltage on the relative humidity was observed. In addition, temporal aspects are discussed in regard to degradation mechanisms. Finally, analytical aspects in regard to storing devices are discussed.

Inline printing and coating methods have been demonstrated to enable a high technical yield of fully roll-to-roll processed polymer tandem solar cell modules. We demonstrate generality by employing different material sets and also describe how the ink systems must be carefully co-developed in order to reach the ambitious objective of a fully printed and coated 14-layer flexible tandem solar cell stack. The roll-to-roll methodologies involved are flexographic printing, rotary screen printing, slot-die coating, X-ray scattering, electrical testing and UV-lamination. Their combination enables the manufacture of completely functional devices in exceptionally high yields. Critical to the ink and process development is a carefully chosen technology transfer to industry method where first a roll coater is employed enabling contactless stack build up, followed by a small roll-to-roll coater fitted to an X-ray machine enabling in situ studies of wet ink deposition and drying mechanisms, ultimately elucidating how a robust inline processed recombination layer is key to a high technical yield. Finally, the transfer to full roll-to-roll processing is demonstrated.