On the stability of a variety of organic photovoltaic devices by IPCE and in situ IPCE analyses--the ISOS-3 inter-laboratory collaboration.

This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPV) devices prepared by leading research laboratories. All devices have been shipped to and degraded at RISØ-DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work, we apply the Incident Photon-to-Electron Conversion Efficiency (IPCE) and the in situ IPCE techniques to determine the relation between solar cell performance and solar cell stability. Different ageing conditions were considered: accelerated full sun simulation, low level indoor fluorescent lighting and dark storage. The devices were also monitored under conditions of ambient and inert (N(2)) atmospheres, which allows for the identification of the solar cell materials more susceptible to degradation by ambient air (oxygen and moisture). The different OPVs configurations permitted the study of the intrinsic stability of the devices depending on: two different ITO-replacement alternatives, two different hole extraction layers (PEDOT:PSS and MoO(3)), and two different P3HT-based polymers. The response of un-encapsulated devices to ambient atmosphere offered insight into the importance of moisture in solar cell performance. Our results demonstrate that the IPCE and the in situ IPCE techniques are valuable analytical methods to understand device degradation and solar cell lifetime.

TOF-SIMS investigation of degradation pathways occurring in a variety of organic photovoltaic devices--the ISOS-3 inter-laboratory collaboration.

The present work is the fourth (and final) contribution to an inter-laboratory collaboration that was planned at the 3rd International Summit on Organic Photovoltaic Stability (ISOS-3). The collaboration involved six laboratories capable of producing seven distinct sets of OPV devices that were degraded under well-defined conditions in accordance with the ISOS-3 protocols. The degradation experiments lasted up to 1830 hours and involved more than 300 cells on more than 100 devices. The devices were analyzed and characterized at different points of their lifetimes by a large number of non-destructive and destructive techniques in order to identify specific degradation mechanisms responsible for the deterioration of the photovoltaic response. Work presented herein involves time-of-flight secondary ion mass spectrometry (TOF-SIMS) in order to study chemical degradation in-plane as well as in-depth in the organic solar cells. Various degradation mechanisms were investigated and correlated with cell performance. For example, photo-oxidation of the active material was quantitatively studied as a function of cell performance. The large variety of cell architectures used (some with and some without encapsulation) enabled valuable comparisons and important conclusions to be drawn on degradation behaviour. This comprehensive investigation of OPV stability has significantly advanced the understanding of degradation behaviour in OPV devices, which is an important step towards large scale application of organic solar cells.

Oxygen-Induced Degradation in C60-Based Organic Solar Cells: Relation Between Film Properties and Device Performance.

Fullerene-based molecules are the archetypical electron-accepting materials for organic photovoltaic devices. A detailed knowledge of the degradation mechanisms that occur in C60 layers will aid in the development of more stable organic solar cells. Here, the impact of storage in air on the optical and electrical properties of C60 is studied in thin films and in devices. Atmospheric exposure induces oxygen-trap states that are 0.19 eV below the LUMO of the fullerene C60. Moreover, oxygen causes a 4-fold decrease of the exciton lifetime in C60 layers, resulting in a 40% drop of short-circuit current from optimized planar heterojunction solar cells. The presence of oxygen-trap states increases the saturation current of the device, resulting in a 20% loss of open-circuit voltage. Design guidelines are outlined to improve air stability for fullerene-containing devices.

Root-cause failure analysis of photocurrent loss in polythiophene:fullerene-based inverted solar cells.

Metal oxide transport layers have played a crucial role in recent progress in organic photovoltaic (OPV) device stability. Here, we measure the stability of inverted and encapsulated polythiophene:fullerene cells with MoO3/Ag/Al composite anode in operational conditions combining solar radiation and 65 °C. Performance loss of over 50% in the first 100 h of the aging is dominated by a drop in the short-circuit current (Jsc). We reveal a concurrent loss in reflectance from 85% to 50% above 650 nm, which is below the optical gap of the used photoactive materials, hence, excluding any major degradation in the bulk of this layer. Correlating the responses of aged devices to a series of test structures comprised of ITO/ZnO cathode, MoO3/Ag, and MoO3/Ag/Al anodes and their combinations with the active layer allowed us to identify that the presence of Al causes the reduced reflectance in these devices, independent of the presence of the active layer. Systematic single-stress aging on the test structures further indicates that elevated heat is the cause of the reflectance loss. Cross-section transmission electron microscopy coupled with elemental analysis revealed the unsuspected role of Al; notably, it diffuses through the entire 150 nm thick Ag layer and accumulates at the MoO3/Ag interface. Moreover, XRD analysis of the aged MoO3/Ag/Al anode indicates the formation of Ag2Al alloy. Depth profiling with X-ray photoelectron spectroscopy advanced our understanding by confirming the formation of Ag-Al intermetallic alloy and the presence of oxidized Al only at the MoO3/Ag interface suggesting a concomitant reduction of MoO3 to most probably MoO2. This latter compound is less reflective than MoO3, which can explain the reduced reflectance in aged devices as proven by optical simulations. On the basis of these results, we could estimate that 20% of the loss in Jsc is ascribed to reduction of MoO3 triggered by its direct contact with Al.

Nafion-modified MoOx as effective room-temperature hole injection layer for stable, high-performance inverted organic solar cells.

We present a hole injection layer processed from solution at room temperature for inverted organic solar cells. Bis(2,4-pentanedionato) molybdenum(VI) dioxide (MoO2(acac)2) is used as the precursor for MoOx. Small amounts of Nafion in the precursor solution allow it to form continuous films with good wetting onto the active layers. The hydrolysis of MoO2(acac)2 and the effects of adding Nafion to the precursor solution are studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The devices with solution-processed MoOx including Nafion exhibited comparable performance to the reference devices based on the commonly used hole injection layers such as poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) or evaporated MoO3. Inverted poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester devices with Nafion-modified MoOx maintain 80% of their initial power conversion efficiency upon exposure to ambient air for ∼5000 h, outperforming devices with PEDOT:PSS or with evaporated MoO3.

Comparative Indoor and Outdoor Degradation of Organic Photovoltaic Cells via Inter-laboratory Collaboration.

We report on the degradation of organic photovoltaic (OPV) cells in both indoor and outdoor environments. Eight different research groups contributed state of the art OPV cells to be studied at Pomona College. Power conversion efficiency and fill factor were determined from IV curves collected at regular intervals over six to eight months. Similarly prepared devices were measured indoors, outdoors, and after dark storage. Device architectures are compared. Cells kept indoors performed better than outdoors due to the lack of temperature and humidity extremes. Encapsulated cells performed better due to the minimal oxidation. Some devices showed steady aging but many failed catastrophically due to corrosion of electrodes not active device layers. Degradation of cells kept in dark storage was minimal over periods up to one year.

Solution-processed MoO3 thin films as a hole-injection layer for organic solar cells.

We report on a sol-gel-based technique to fabricate MoO(3) thin films as a hole-injection layer for solution-processed or thermally evaporated organic solar cells. The solution-processed MoO(3) (sMoO(3)) films are demonstrated to have equal performance to hole-injection layers composed of either PEDOT:PSS or thermally evaporated MoO(3) (eMoO(3)), and the annealing temperature at which the sol-gel layer begins to work is consistent with the thermodynamic analysis of the process. Finally, the shelf lifetime of devices made with the sMoO(3) is similar to equivalent devices prepared with a eMoO(3) hole-injection layer.